Silver halide photographic materials

ABSTRACT

Disclosed is a silver halide photographic material containing a compound of a general formula (1) or (2): 
     
         ED-(Time).sub.t -Y-L-Z                                     (1) 
    
     wherein ED represents a group that releases the moiety (Time) t  -Y-L-Z by reaction with an oxidation product of a developing agent; Time represents a divalent linking group; t represents 0 or 1; Y represents a divalent group comprising a hetero atom through which Y bonds to the moiety ED-(Time) t  ; L represents a divalent group which is capable of being cleaved by reaction with components in a developer; and Z represents a monovalent functional group that expresses a development inhibiting effect; ##STR1## wherein Time, t, L and Z have the same meanings as above; Y represents a divalent group comprising a hetero atom through which Y bonds to the moiety ##STR2## R 1  represents an aliphatic group or an aromatic group; G 1  represents is ##STR3## G 2  represents a mere bond, --O--, --S-- or ##STR4## R 2  has the same meaning as R 1  or represents a hydrogen atom; when the compound has plural R 2  &#39;s, they may be same as or different from each other; and one of A 1  and A 2  represents a hydrogen atom, and the other represents a hydrogen atom, or an acyl group, an alkylsulfonyl group or an arylsulfonyl group. The material may reproduce excellently a line original to form an ultra-hard image having a high background density. It also has a broad exposure latitude in halftone dot image-taking work and can form an ultra-hard halftone dot image with a high image quality. The material is useful in formation of ultra-hard negative images by photomechanical process.

FIELD OF THE INVENTION

The present invention relates to silver halide photographic materialsand a method for forming an ultra-hard negative image with thematerials. More specifically, it relates to ultra-hard negativephotographic materials of high sensitivity which can be used in aphotomechanical process for forming hard negative images.

BACKGROUND OF THE INVENTION

In the field of photomechanical process technology, photographicmaterials with excellent original-producibility, stable processingsolutions and a simplified replenishment system are required for dealingwith diversified and complicated print forms currently in use.

Originals employed in a line work process often are composed ofphototypeset letters, hand-written letters, illustrations and halftonedot image photographs. Accordingly, the original contains plural imagesdiffering concentration and differing line width in combination.Photomechanical cameras and photographic materials capable of finishingthe images from such originals with good reproducibility, as well asimage-forming methods applicable to such photographic materials aredesired earnestly. On the other hand, for the photomechanical process ofproducing catalogs or large-sized posters, blow-up or reduction of dotimage photographs is effected widely. In the photomechanical process ofusing enlarged dot images, the dots are coarsened to give blurredphotoprints. As opposed to this, in the photomechanical process forforming reduced photoprints, fine dots with an enlarged ratio oflines/inch are photographed. Accordingly, an image-forming method withmuch broader latitude is desired for the purpose of maintaining thereproducibility of halftone dot images in the photomechanical process.

As the light source for a photomechanical camera, a halogen lamp orxenon lamp is employed. To obtain sufficient photographing sensitivityto the light source, the photographic material employed in thephotomechanical process is generally ortho-sensitized. However, it wasfound that ortho-sensitized photographic materials are influencedgreatly by the chromatic aberration of a lens and therefore the qualityof the images frequently is worsened by such an influence. It wasfurther found that the deterioration of image quality is more noticeablewhen a xenon lamp is used as the light source.

As a system of attempting to satisfy the demand for broad latitude, amethod is known where a lith-type silver halide photographic materialcomposed of silver chlorobromide (having a silver chloride content of atleast 50% or more) is processed with a hydroquinone-containing developerwhere the effective concentration of the sulfite ion therein is loweredextremely (generally, to 0.1 mol/liter or less) to obtain thereby a lineimage or halftone dot image having a high contrast and a high blackeneddensity where the image portions and the non-image portions are clearlydifferentiated from each other. However, the method has variousdrawbacks. Precisely, since the sulfite concentration in the developeris low, development is extremely unstable to air oxidation. For thepurpose of stabilizing the activity of the processing solution, variousmeans are effected. The processing speed is extremely slow and theworking efficiency is poor.

Accordingly, an improved image-forming system is desired which is freefrom the instability of the image formation in the above-mentioneddevelopment method (lith-development system) and which may be processedwith a processing solution having an excellent storage stability to givephotographic images having ultra-hard photographic characteristics. Asone example, a system of forming an ultra-hard negative image having agamma value of more than 10 has been proposed, for example, in U.S. Pat.Nos. 4,166,742, 4,168,977, 4,221,857, 4,224,401, 4,243,739, 4,272,606and 4,311,781, where a surface latent image-type silver halidephotographic material containing a particular acryl hydrazine compoundis processed with a developer which has an excellent storage stabilityand which contains a sulfite preservative in an amount of 0.15 mol/literor more, under the condition of a pH value of from 11.0 to 12.3. Theproposed image-forming system has the characteristic aspect that asilver iodobromide or silver chloroiodobromide-containing photographicmaterial can be processed, although only a high silver chloridecontent-having silver chlorobromide photographic material can beprocessed by the conventional ultra-hard image-forming method.

The proposed image-forming system is excellent in that an image with asharp halftone dot image quality is formed, the process proceeds stablyat a high speed and the reproducibility of the original used is good.However, a further improved system with a further elevated originalreproducibility is desired still for the purpose of satisfactorilydealing with the diversified print forms currently in use.

JP-A-61-213847 (the term "JP-A" as used herein means an "unexaminedpublished Japanese patent application") and U.S. Pat. No. 4,684,604disclose photographic materials containing a redox compound capable ofreleasing a development inhibitor by oxidation in an attempt atbroadening the latitude of reproduction of gradation of images. However,where such a redox compound is added to a photographic material to beprocessed in an ultra-hard processing system using a hydrazinederivative in an amount sufficient for satisfactorily improving thereproducibility of reproducing both line images and halftone images, apart of the development inhibitor released from the redox compound wouldflow into the processing solution for development. As a result, when alarge amount of such a photographic material containing a redox compoundof the kind is processed continuously, the released developmentinhibitor would accumulate in the developer tank. When development iscontinued with such a fatigued developer, the formation of hard imagesis impossible and the sensitivity of the photographic materials beingprocessed is decreased. In particular, where one automatic developingmachine is used for processing photographic materials containing such aredox compound and also for processing other various picture-takingphotographic materials, contact-printing photographic materials,scanning photographic materials and photocomposing photographicmaterials, there occurs a problem that the development inhibitor asreleased from the redox compound often has a bad influence on thephotographic properties of other photographic materials.

Because of these reasons, the amount of the redox compound used islimited so that the effect of the redox compound is not displayedsufficiently, or the photographic material having such a redox compoundmust be processed with specifically defined processing solutions andonly in a specifically closed system. Such limitation or use of such aclosed system is inconvenient.

SUMMARY OF THE INVENTION

The first object of the present invention is to provide novel compoundswhich have an excellent storage stability and rapidly release adevelopment inhibitor.

The second object of the present invention is to provide novel compoundswhich can be used in a hard photographic material system in an amountsufficient for improving the image reproducibility without fatiguing thedeveloper.

The third object of the present invention is to provide a photographicmaterial for photomechanical processes, which can be processed with ahighly stable developer to give a hard image.

The fourth object of the present invention is to provide a hardphotographic material for photomechanical processes, which contains ahydrazine nucleating agent and which forms a halftone image with a broadhalftone gradation.

The fifth object of the present invention is to provide a photographicmaterial for photomechanical processes, which can be processed stably bycontinuous processing with a running solution.

These objects were attained by a silver halide photographic materialcontaining a compound of general formula (1):

    ED-(Time).sub.t -Y-L-Z                                     (1)

wherein ED represents a group that releases the moiety (Time)_(t) -Y-L-Zby reaction with an oxidation product of a developing agent; Timerepresents a divalent linking group; t represents 0 or 1; Y represents adivalent group comprising a hetero atom through which Y bonds to themoiety ED-(Time)_(t) -; L represents a divalent group which is capableof being cleaved by reaction with components of a developer; and Zrepresents a functional group that expresses a development inhibitingeffect.

In a preferred embodiment, the group ED in formula (1) comprises a redoxgroup having a hydrazine structure and releasing the moiety (Time)_(t)-Y-L-Z by oxidation with an oxidation product of a developing agent.

The objects were also attained by a silver halide photographic materialcontaining a compound of general formula (2): ##STR5## wherein Time, t,L and Z have the same meanings as defined in formula (1); Y represents adivalent group comprising a hetero atom through which Y bonds to themoiety ##STR6## R₁ represents an aliphatic group or an aromatic group;G₁ represents ##STR7## --SO--, --SO₂ --, or ##STR8## G₂ represents amere bond, or --O--, --S-- or ##STR9## R₂ has the same meaning as R₁ orrepresents a hydrogen atom; when the molecule has plural R₂ 's, they maybe the same or different; and one of A₁ and A₂ represents a hydrogenatom, and the other represents a hydrogen atom, an acyl group having 2to 10 carbon atoms, preferably 1 to 6 carbon atoms, e.g., acetyl, analkylsulfonyl group having 1 to 10 carbon atoms, preferably 1 to 6carbon atoms, e.g., methyl sulfonyl or an arylsulfonyl group having 6 to15 carbon atoms, preferably 6 to 10 carbon atoms, e.g., phenylsulfonyland p-tolylsulfonyl.

As another preferred embodiment, the silver halide photographic materialmay contain a hydrazine compound which is different from compounds offormulae (1) and (2) in an image-forming layer containing a silverhalide emulsion or in any other hydrophilic colloid layer such as theadjacent hydrophilic colloid layer.

BRIEF DESCRIPTION OF THE DRAWING

FIGURE shows one constitutional embodiment of forming super-imposedletter images by contact exposure, where (a) is a transparent orsemitransparent support, (b) is a line original in which the blackportions indicate line images, (c) is a transparent or semitransparentsupport, (d) is a halftone original in which the black portions indicatedot images, and (e) is a dot-to-dot working photographic material inwhich the shadow portion indicates a light-sensitive layer.

DETAILED DESCRIPTION OF THE INVENTION

In formula (1), the group represented by ED is one which can release themoiety (Time)_(t) -Y-L-Z by reaction with an oxidation product of adeveloping agent. More specifically, it is a group releasing the moiety(Time)_(t) -Y-L-Z by a coupling reaction with an oxidation product of anaromatic amine developing agent, or a redox group which is firstoxidized with an oxidation product of a developing agent of variouskinds and then releases the moiety (Time)_(t) -Y-L-Z via the successiveone-stage or plural-stages reaction.

Preferably, ED is a redox group. Preferred examples of such a redoxgroup of ED include hydroquinones, catechols, naphthohydroquinones,aminophenols, pyrazolidones, hydrazines, hydroxylamines and reductones.Hydrazines are especially preferred.

In formula (2), the aliphatic group represented by R₁ is preferably onehaving from 1 to 30 carbon atoms, and especially preferably a linear,branched or cyclic alkyl group having from 1 to 20 carbon atoms. Thealkyl group optionally may have substituent(s).

In formula (2), the aromatic group represented by R₁ is a monocyclic orbicyclic aryl or unsaturated heterocyclic group. The unsaturatedheterocyclic group optionally may be condensed with an aryl group toform a heteroaryl group.

For example, the aromatic group is preferably one derived from benzenerings, naphthalene rings, pyridine rings, quinoline rings andisoquinoline rings. Especially preferred is an aromatic group thatcontains a benzene ring.

R₁ is preferably an aryl group.

The aryl group or unsaturated heterocyclic group represented by R₁optionally may be substituted. Typical examples of substituents for sucha substituted aryl or unsaturated heterocyclic group include an alkylgroup, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxygroup, an aryl group, a substituted amino group, a ureido group, aurethane group, an aryloxy group, a sulfamoyl group, a carbamoyl group,an alkylthio group, an arylthio group, a sulfonyl group, a sulfinylgroup, a hydroxyl group, a halogen atom, a cyano group, a sulfone group,an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, anacyloxy group, a carbonamido group, a sulfonamido group, a carboxylgroup and a phosphorylamido group. Preferred substituents are a linear,branched or cyclic alkyl group (preferably having from 1 to 20 carbonatoms), an aralkyl group (preferably having from 7 to 30 carbon atoms),an alkoxy group (preferably having from 1 to 30 carbon atoms), asubstituted amino group (preferably an amino group substituted by alkylgroup(s) each having from 1 to 30 carbon atoms), an acylamino group(preferably having from 2 to 40 carbon atoms), a sulfonamido group(preferably having from 1 to 40 carbon atoms), a ureido group(preferably having from 1 to 40 carbon atoms) and a phosphorylamidogroup (preferably having from 1 to 40 carbon atoms).

In formula (2), G₁ is preferably ##STR10## or --SO₂ --, and is mostpreferably ##STR11## A₁ and A₂ are preferably hydrogen atoms.

In formulae (1) and (2), Time represents a divalent linking group, whichmay have a timing-regulating function. The divalent group represented byTime is one which releases the moiety Y-L-Z from the moiety Time-Y-L-Zas released from ED, via a one-step or plural-step reaction.

Examples of the divalent linking group of Time include p-nitro-phenoxyderivatives releasing the moiety Y-L-Z by an intramolecular ring-closurereaction as described in U.S. Pat. No. 4,248,962 (JP-A-54-145135);compounds releasing the moiety Y-L-Z by a ring-cleavage reactionfollowed by an intramolecular ring-closure reaction as described in U.S.Pat. Nos. 4,310,612 (JP-A-55-53330) and 4,358,252; succinic acidmonoesters or analogues thereof releasing the moiety Y-L-Z by anintramolecular ring-closure reaction of the carboxyl group along withformation of an acid anhydride as described in U.S. Pat. Nos. 4,330,617,4,446,216 and 4,483,919 and JP-A-59-121328; compounds releasing themoiety Y-L-Z by electron transfer of the aryloxy or heterocyclic-oxygroup via the conjugated double bond to form a quinomonomethane or ananalogue thereof as described in U.S. Pat. Nos. 4,409,232, 4,421,845,RESEARCH DISCLOSURE Item No. 2,228 (December, 1981), U.S. Pat. No.4,416,977 (JP-A-57-135944) and JP-A-58-209736 and JP-A-58-209738;compounds releasing the moiety Y-L-Z by electron transfer of the enaminestructure moiety of the nitrogen-containing hetero ring from thegamma-position of the enamine as described in U.S. Pat. No. 4,420,554(JP-A-57-136640), and JP-A-57-135945, JP-A-57-188023, JP-A-58-98728 andJP-A-58 -209737; compounds releasing the moiety Y-L-Z by anintramolecular ring-closure reaction of the hydroxyl group as formed byelectron transfer of the carbonyl group as conjugated with the nitrogenatom of the nitrogen-containing hetero ring, as described inJP-A-57-56837; compounds releasing the moiety Y-L-Z with formation ofaldehydes as described in U.S. Pat. No. 4,146,396 (JP-A-52-90932) andJP-A-59-93442, JP-A-59-75475, JP-A-60-249148 and JP-A-60-249149;compounds releasing the moiety Y-L-Z with decarbonylation of thecarboxyl group as descried in JP-A-51-146828, JP-A-57-179842 andJP-A-59-104641; compounds having -O-COOCR_(a) R_(b) -Y-L-Z (whereinR_(a) and R_(b) each represents a monovalent group) and releasing themoiety Y-L-Z by decarbonylation followed by formation of aldehydes;compounds releasing the moiety Y-L-Z with formation of isocyanates asdescribed in JP-A-60-7429; and compounds releasing the moiety Y-L-Z by acoupling reaction with the oxidation product of a color developing agentas described in U.S. Pat. No. 4,438,193.

Examples of divalent linking groups of Time are also described in detailin JP-A-61-236549, JP-A-1-269936 and Japanese Patent Application No.2-93487.

In formulae (1) and (2), the divalent group represented by Y has heteroatom(s) and is bonded to the moiety of ED-(Time)_(t) - in formula (1) orto the moiety of ##STR12## in formula (2) via the hetero atom.

The group represented by -Y-L-Z in formula (1) or (2) is preferably onerepresented by the following formula (3) or (4). It is especiallypreferably the group of formula (4).

    -Y.sub.1 -Y.sub.2 -L-Z                                     (3)

wherein Y₁ represents --O--, --S--, --Se--, --Te-- or ##STR13## R₃represents a hydrogen atom or has the same meaning as R₁ in formula (2);Y₂ represents an aliphatic group having 1 to 20 carbon atoms, preferably1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms or anaromatic group having 2 to 20 carbon atoms, preferably 3 to 15 carbonatoms, and more preferably 5 to 10 carbon atoms, or it can also be adivalent group formed by combination of such an aliphatic or aromaticgroup and --O--, --S--, --Se--, ##STR14## (wherein R₄ has the samemeaning as R₃), --CO--, --SO-- or --SO₂ --. The group of Y₂ optionallymay be substituted, and the total number of carbon atoms of Y₂ is 1 to30, preferably 1 to 20 and more preferably 1 to 15. Preferred examplesof substituents for Y₂ are the same as those for R₁.

L and Z have the same meanings as those in formulae (1) and (2).##STR15## wherein L and Z have the same meanings as in formulae (1) and(2); Y₄ represents a single bond or has the same meaning as Y₂ informula (3); and Y₃ represents a non-metallic atomic group that forms anitrogen-containing hetero ring with the nitrogen atom in the formula.

In formula (4), the nitrogen-containing hetero ring represented by:##STR16## is preferably a heterocyclic aromatic ring, and morepreferably a 5-membered or 6-membered ring which can be either amonocyclic group or a condensed ring and which may be substituted.

Typical examples of preferred heterocyclic aromatic rings are pyrroles,imidazoles, pyrazoles, 1,2,3-triazoles, 1,2,4-triazoles, tetrazoles,2-thioxathiazolines, 2-oxathiazolines, 2-thioxaoxazolines,2oxaoxazolines, 2-thioxaimidazolines, 2-oxaimidazolines,3-thioxa-1,2,4-triazolines, 3-oxa-1,2,4-triazolines,1,2-oxazoline-5-thiones, 1,2-thiazoline-5-thiones, 1,2-oxazolin-5-ones,1,2-thiazolin-5-ones, 2-thioxa-1,3,4-thiadiazolines,2-oxa-1,3,4-thiadiazolines, 2-thioxa-1,3,4-oxadiazolines,2-oxa-1,3,4-oxadiazolines, 2-thioxadihydropyridines,2-oxadihydropyridines, 4-thioxadihydropyridines, 4-oxadihydropyridines,isoindoles, indoles, indazoles, benzotriazoles, benzimidazoles,2-thioxabenzimidazoles, 2-oxabenzimidazoles, benzoxazoline-2-thiones,azaindenes, benzoxazolin-2-ones, benzothiazoline-2-thiones,benzothiazolin-3-ones, carbazoles, purines, carbolines, phenoxazines andphenothiazines; as well as condensed heterocyclic aromatic rings havingcondensed ring(s) at various position(s), such as pyrazolopyridines,pyrazolopyrimidines, pyrazolopyrroles, pyrazolopyrazoles,pyrazoloimidazoles, pyrazoloxazoles, pyrazolothiazoles,pyrazolotriazoles, imidazolopyridines, imidazolopyrimidines,imidazolopyrroles, imidazoloimidazoles, imidazoloxazoles,imidazolothiazoles and imidazolotriazoles.

More preferred examples of such heterocyclic aromatic rings arepyrroles, pyrazoles, triazoles, tetrazoles, 2-thioxathiazolines,2-thioxaoxazolines, indoles, indazoles, benzotriazoles, benzimidazoles,2-thioxa-1,3,4-thiadiazolines, azaindenes, 5-thioxatetrazolines,2-thioxa-1,3,4-oxadiazolines, and 2-thioxa-1,2,4-triazolines; as well ascondensed heterocyclic aromatic rings having condensed ring(s) atvarious position(s), such as pyrazolopyridines and pyrazoloimidazoles.Especially preferred are pyrazole skeleton-containing heterocyclicaromatic rings such as pyrazoles, indazoles and pyrazolopyridines.

The heterocyclic compounds may optionally be substituted. Examples ofsubstituents for such compounds include a mercapto group, a nitro group,a carboxyl group, a sulfo group, a phosphono group, a hydroxyl group, analkyl group, an aralkyl group, an alkenyl group, an alkynyl group, anaryl group, an alkoxy group, an aryloxy group, an amino group, anacylamino group, a sulfonylamino group, an ureido group, an urethanegroup, a sulfamoyl group, a carbamoyl group, an alkylthio group, anarylthio group, a sulfonyl group, a sulfinyl group, a halogen atom, acyano group, an aryloxycarbonyl group, an acyl group, an alkoxycarbonylgroup, an acyloxy group, a carbonamido group, a sulfonamido group and aphosphonamido group.

In formulae (1) and (2), the group represented by L is one which may becleaved by reaction with components of a developer. Examples ofcomponents of a developer which cleave the group L are compounds whichare contained in an ordinary developer, such as alkali substances,hydroquinones and sulfite ions, as well as surfactants, amines and saltsof organic acids. To effect cleavage of the group L, particular reagentssuch as fluoride ions, hydrazines and hydroxylamines may be added to adeveloper. The group L may be cleaved by the complex reaction of thecomponents.

In the compounds of formula (1) or (2), the moiety Y-L-Z is released byreaction with an oxidation product of a developing agent (and thesuccessive reaction), in accordance with the reaction scheme mentionedbelow. Where the moiety Y-L-Z is released in the step of development, itis desired that the reaction of cleavage of L by the components of adeveloper (the reaction being represented by Y-L-Z→Y-L₁ +L₂ -Z) occurssubstantially after the reaction of releasing the moiety Y-L-Z. Inaddition, since it is desired that the cleavage of the group L occurssubstantially after the release of the moiety Y-L-Z, the reaction isoften confounded with the reaction of the divalent linking grouprepresented by Time in formula (1) or (2). However, in the reaction ofthe group Time, release of the moiety Time-Y-L-Z from the compound isthe essential factor of the successive reaction of releasing the moietyY-L-Z from the moiety Time-Y-L-Z. That is to say, the moiety Y-L-Z isreleased substantially only after release of the moiety Time-Y-L-Z. Asopposed to this, it is desired that cleavage of the group L occursirrespective of the release of the moiety Y-L-Z. That is to say,cleavage of the group L may occur by the action of the components of adeveloper even in the absence of release of Time-Y-L-Z or Y-L-Z.##STR17## As shown above, where it is represented that Y-L-Z isconverted into Y-L₁ and L₂ -Z by cleavage of L, it is desired that L₂contains an anionic functional group. More preferably, L₂ contains aconjugated base of an acidic functional group having a pKa of 6 or lessas a functional group, and especially preferably a conjugated base of anacidic functional group having a pKa of 5 or less as a functional group.Preferred examples of such functional groups are a carboxyl group, asulfonic acid group, a sulfinic acid group, a phosphoric acid group, aphosphonic acid group and a phosphinic acid group. It is desired thatsuch a functional group is formed by cleavage of the group L.

In formulae (1) and (2), the group represented by L-Z is preferably oneof the following formulae (5) to (8) wherein Z has the same meaning asthat in formulae (1) and (2).

    -L.sub.3 -L.sub.4 -Z

wherein L₃ represents ##STR18## --O--SO₂ --, ##STR19## R₅ represents ahydrogen atom or has the same meaning as R₁ in formula (2); L₄ has thesame meaning as Y₄ in formula (4); and Z has the same meaning as that informulae (1) and (2). ##STR20## wherein L₅ represents ##STR21## --SO₂--; L₆ represents a monovalent group, and two L₆ 's may be the same ordifferent or may be bonded to each other to form a ring; or one or bothof the two L₆ 's may be bonded to the group Y of formula (1) or (2) toform a ring or a polycyclic ring; L₇ represents --O--, --S-- or --SO₂--; L₄ has the same meaning as that in formula (5); and Z has the samemeaning as that in formulae (1) and (2). ##STR22## wherein L₄, L₅, L₆,L₇ and Z have the same meanings as those in formula (6). ##STR23##wherein L4 has the same meaning as in formula (5); Z has the samemeaning as in formulae (1) and (2); L₅ has the same meaning as informula (6); L₈ has the same meaning as Y₁ in formula (3); and L₉represents a nonmetallic atomic group necessary for forming a 5- or6-membered cyclic structure together with the nitrogen atom, L₅ andcarbonyl group in the formula.

In formulae (1) and (2), the group represented by Z is a functionalgroup that expresses a development inhibiting activity. Preferably, Zrepresents a development inhibitor in the form of Y-L-Z. After cleavageof L, the resulting L₂ -Z is a compound having a small developmentinhibiting activity. If desired, Z may form together with the group Y informula (1) or (2) any bond other than the bond via L therebetween.Thus, Y, L and Z form a cyclic structure which is opened by cleavage ofL.

Y-L-Z preferably represents a development inhibitor. Examples of knownconventional development inhibitors are described, for example, in T. H.James, The Theory of Photographic Processes, 4th Ed. (published byMacmillan Co., 1977), pages 396 to 399 and in Japanese PatentApplication No. 2-93487, pages 56 to 69.

Such development inhibitors are preferably substituted. Examples ofsubstituents are the above-mentioned substituents for R₁ in formula (2).The substituents may be substituted further.

The development inhibitors of Y-L-Z which are used in the presentinvention, are especially preferably compounds capable of inhibitingnucleating infectious development.

Nucleating infectious development is a novel development chemistry whichhas been employed in image formation with the Fuji Film GRANDEX System(by Fuji Photo Film Co., Ltd.) or with the Kodak Ultratec System (byEastman Kodak Co., Ltd.).

The novel development chemistry, described in Journal of JapanPhotographic Association, Vol. 52, No. 5, pages 390 to 394 (1989) andJournal of Photographic Science, Vol. 35, page 162 (1987), is composedof a development step where exposed silver halide grains are exposedwith an ordinary developing agent and the successive nucleatinginfectious development step where the oxidation product of thedeveloping agent as formed in the previous development step is oxidizedwith a nucleating agent by cross-oxidation to form an active nucleatingseed, and the ambient non-exposed or weakly exposed silver halide grainsare developed with the resulting active seeds by nucleating infectiousdevelopment.

Accordingly, since the complete development step is composed of anordinary development step and the successive nucleating infectiousdevelopment step, novel compounds capable of retarding the nucleatinginfectious development step may display a development inhibitingactivity in addition to the conventional ordinary development inhibitorswhich have heretofore been known and used in the system. The formernovel compounds are herein referred to as nucleating developmentinhibitors.

The development inhibitor of Y-L-Z used in the present invention ispreferably a nucleating development inhibitor. Accordingly, thefunctional group of Z, which expresses a development inhibiting effect,is also preferably a functional group of expressing an effect ofinhibiting nucleating infectious development. Typical examples of groupsof Z of expressing such an effect of inhibiting nucleating infectiousdevelopment are advantageously conventional mercapto group and azolegroups. Preferably, Z is a nitro group; a nitroso group; anitrogen-containing heterocyclic group, especially a 6-memberednitrogen-containing heterocyclic aromatic group, such as one derivedfrom pyridines, pyrazines or quinolines; a functional group having anN-halogen bond; a group derived from quinones, tetrazolium compounds oramine oxides; an azoxy group; or a group derived from a coordinationcompound having an oxidizing potency.

Especially preferred are a nitro group and a pyridine group.

Where Z is a nitro group, L preferably contains an aromatic ring as thepartial structure of itself and it is preferred that Z is bonded to thearomatic ring moiety of L.

Y-L-Z as used in the present invention means a development inhibitor,and it may be considered that Y-L-Z contains a development inhibitingmoiety and a moiety to be released from GI or Time along with a moietyof cleaving from the molecule by reaction with components in adeveloper, as the partial structure thereof.

As the development inhibiting moiety of Y-L-Z, a structure of any knowndevelopment inhibitor may be employed.

Specific examples of nucleating development inhibitor moieties which canbe used in the present invention are described below.

1. Nitro group-containing compounds (including those having a nitrogroup(s) at any possible positions):

(1) Nitrobenzene, Nitrotoluene;

(2) Dinitrobenzene, Dinitrotoluene;

(3) Nitrobenzoates;

(4) Dinitrobenzoates;

(5) Nitrobenzoic acid amides;

(6) Dinitrobenzoic acid amides

(7) Nitronaphthalenes;

(8) Nitropyrazoles;

(9) Nitroimidazoles;

(10) Nitropyrroles;

(11) Mono- or di-nitroindoles;

(12) Mono- or di-nitroindazoles;

(13) Mono or di-nitrobenzimidazoles;

(14) Nitrobenzotriazoles;

(15) Nitropyridines;

(16) Nitropyrimidines;

(17) Nitrobenzothiazoles;

(18) Nitrobenzoxazoles;

(19) Nitroquinolines;

(20) Nitrotetrazaindenes;

2. Nitroso group-containing compounds (including those having a nitrosogroup(s) at any possible positions):

(1) Nitrosobenzenes, dinitrosobenzenes;

(2) Nitrosonaphthalenes, dinitrosonaphthalenes;

(3) Nitrosopyridines;

(4) Nitrosopyrimidines;

(5) N-nitrosoanilines;

(6) N-nitrosoacetanilides;

(7) N-nitroso-2-oxazolidones;

(8) N-nitroso-N-benzyltoluenesulfonamides.

3. Nitrogen-containing hetero rings:

(1) Pyridines;

(2) Nicotinates, Nicotinic acid amides;

(3) Isonicotinates, Isonicotinic acid amides;

(4) Pyrazines;

(5) Indolidines;

(6) Quinolidines;

(7) Quinolines;

(8) Isoquinolines;

(9) Phthalazines;

(10) Naphthidines;

(11) Quinoxalines;

(12) Quinazolines;

(13) Phthalidines;

(14) Carbazoles;

(15) Phenanthridines;

(16) Acridines;

(17) Phenanthrolines;

(18) Phenatidines;

(19) Phenothiazines;

(20) Phenarsazines.

4 N-halogen bond-having compounds:

(1) N-chlorosuccinic acid imides.

5. Quinones:

(1) Benzoquinones;

(2) Chlorobenzoquinones;

(3) Naphthoquinones;

(4) Anthraquinones.

6. Tetrazoliums:

(1) 2,3,5-triphenyltetrazolium chlorides.

7. Amine oxides:

(1) Pyridine oxides;

(2) Quinoline oxides.

8 Azoxy compounds:

(1) Azoxybenzenes.

9. Oxidizing potency-having coordination compounds:

(1) EDTA-Fe(III) complexes.

The nulceating development inhibiting moiety employed in the presentinvention advantageously contains a structure derived from theabove-mentioned compounds and other development inhibitors as a partialstructure thereof. In particular, it is preferred that the group ofY-L-Z in formula (1) or (2) contains a residue derived from theillustrated compounds as a partial structure thereof. The nucleatingdevelopment inhibitors employable in the present invention optionallymay be substituted.

Examples of preferred substituents for the nucleating developmentinhibitors include the following groups which may be substitutedfurther.

For instance, there are mentioned an alkyl group, an aralkyl group, analkenyl group, an alkynyl group, an alkoxy group, an aryl group, asubstituted amino group, an acylamino group, a sulfonylamino group, aureido group, a urethane group, an aryloxy group, a sulfamoyl group, acarbamoyl group, an alkylthio group, an arylthio group, a sulfonylgroup, a sulfinyl group, a hydroxyl group, a halogen atom, a cyanogroup, a sulfo group, an alkyloxycarbonyl group, an aryloxycarbonylgroup, an acyl group, an alkoxycarbonyl group, an acyloxy group, acarbonamido group, a sulfonamido group, a carboxyl group, a sulfoxygroup, a phosphono group, a phosphinyl group and a phosphonylamidogroup.

ED or Time in formula (1) or R₁ or Time in formula (2) may contain aballast group therein, which is ordinarily contained in passive (orinactive) photographic additives such as couplers, or may also contain agroup therein, which may promote adsorption of the compound of formula(1) or (2) to silver halides.

Such a ballast group is an organic group which may impart a sufficientmolecular weight to the compound of formula (1) or (2) in order that thecompound could not diffuse substantially to other layers or toprocessing solutions, and it is composed of one or more of an alkylgroup, an aryl group, a heterocyclic group, an ether group, a thioethergroup, an amido group, a ureido group and a sulfonamido group. Apreferred example of such a ballast group is one having substitutedbenzene ring(s); and a ballast group having benzene ring(s) substitutedwith branched alkyl group(s) is especially preferred.

Examples of the other group capable of promoting absorption of thecompound of formula (1) or (2) to silver halides include, for example,cyclic thioamido groups such as 4-thiaozline-2-thione,4-imidaozline-2-thione, 2-thiohydantoin, rhodanine, thiobarbituric acid,tetrazoline-5-thione, 1,2,4-triazoline-3-thione,1,3,4-oxazoline-2-thione, benzimidazoline-2-thione,benzoxazoline-2-thione, benzothiazoline-2-thione, thiotriazine and1,3-imidaozline-2-thione; linear thioamido groups; aliphatic mercaptogroups; aromatic mercapto groups; heterocyclic mercapto groups (when anitrogen atom is adjacent to the carbon atom bonded to --SH, the groupshave the same meaning as the cyclic thioamido groups which are tautomersof the groups, and specific examples of the groups are the same as thosedescribed above); disulfido bond-containing groups, 5-membered or6-membered nitrogen-containing heterocyclic groups composed of acombination of nitrogen, oxygen, sulfur and carbon atoms, such asbenzotriazoles, triazoles, tetrazoles, indazoles, benzimidazoles,imidazoles, benzothiazoles, thiazoles, thiazolines, benzoxazolines,oxazoles, oxazolines, thiadiazoles, oxathiazoles, triazines andazaindenes; as well as heterocyclic quaternary salts such asbenzimidazoliums.

The groups may further be substituted by appropriate substituent(s), ifdesired.

Examples of the substituents include those described for the group R₁ inthe above-described formula (2).

Specific examples of the compounds of the above-described formulae (1)or (2) which can be used in the present invention are described below,but the present invention is not limited thereto. In the formulae, thegroup ##STR24## represents --C(CH₃)₂ --CH₂ --CH₃. ##STR25##

Compounds of formula (2) for use in the present invention are producedin accordance with the routes described below. More specifically, twoequivalents of the corresponding Z-L-Y-(Time)_(t) -H are reacted withtrichloromethyl chlorocarbonate in an organic solvent such asterehydrofuran (THF) in the presence of a base such as triethylamine togive a symmetric carbonyl compound and thereafter the resulting carbonylcompound is reacted with a corresponding hydrazine compound to producethe desired compound of formula (2) (Production Route-1); or acorresponding Z-L-Y-(Time)_(t) -H is condensed with p-nitrophenylchlorocarbonate in the presence of a base and thereafter reacted with acorresponding hydrazine compound to produce the desired compound offormula (2) (Production Route-2).

PRODUCTION ROUTE 1: ##STR26## PRODUCTION ROUTE-2: ##STR27##

Concrete methods for producing the compounds for use in the presentinvention are described, for example, in JP-A-61-213847, JP-A-62-260153,JP-A-3-39953, Jp-A-3-39951 and 3-39949. An example of producing one ofsuch compounds is presented below.

PRODUCTION OF COMPOUND NO. 14: (i) Production of1-t-butoxycarbonyl-4-β-hydroxyethylpyrazole (1):

31.9 ml of triethylamine and 50.0 g of di-tert-butyl dicarbonate wereadded to a mixture comprising 25.7 g of 4-β-hydroxypyrazole and 100 mlof acetonitrile and stirred for 2 days at room temperature. Theresulting blend was poured into 500 ml of an aqueous solution ofhydrochloric acid of the same molar amount as triethylamine and thenextracted with ethyl acetate. Anhydrous magnesium sulfate was addedthereto for drying, and ethyl acetate was removed by distillation underreduced pressure. As a result, compound (1) was obtained as a colorlesstar, with a yield of 21.6 g.

(ii) Production of Compound (2) ##STR28##

A solution of 20.4 g of p-nitrobenzoyl chloride dissolved in 100 ml oftetrahydrofuran was added to a mixture comprising 21.6 g of compound(1), 100 ml of tetrahydrofuran and 15.3 ml of triethylamine in anitrogen atmosphere at -5° C. to 5° C. The temperature of the resultingmixture was gradually elevated up to room temperature and then stirredfor 4 hours. Afterwards, the resulting blend was poured into water andthe solid that precipitated was taken out by filtration. The thusobtained solid was purified by column chromatography to obtain compound(2) with a yield of 24.4 g.

(iii) Production of Compound (3) ##STR29##

30 ml of trifluoroacetic acid was added to 24.4 g of compound (2) andstirred for 4 hours at room temperature. Then the resulting blend waspoured into water and the solid that precipitated was taken out byfiltration and dried. As a result, compound (3) was obtained with ayield of 21.0 g.

Production of Compound No. 14

2.45 ml of trichloromethyl chloroformate was added to a mixturecomprising 21.0 g of compound (3) and 100 ml of tetrahydrofuran in anitrogen atmosphere at -5° C. to 0° C., and subsequently a solution of11.2 ml of triethylamine as dissolved in 50 ml of tetrahydrofuran wasadded thereto. The temperature of the resulting blend was then graduallyelevated up to room temperature and then was stirred for 4 hours. Next,the reaction mixture was again cooled, 21.7 g of a compound of:##STR30## was added thereto and subsequently 5.60 ml of triethylaminewas added thereto. The temperature of the resulting blend was thengradually elevated up to room temperature and was stirred for a further12 hours. The reaction mixture was poured into water and extracted withethyl acetate. The organic layer was concentrated to dryness. The dryresidue obtained was purified by silica gel chromatography to obtain theintended product with a yield of 15.0 g. The chemical structure of theproduct was identified by NMR spectrum, IR spectrum and elementaryanalysis.

The compounds of the present invention are used in an amount in therange of from 1×10⁻⁶ to 5×10⁻² mol, more preferably from 1×10⁻⁵ to1×10⁻² mol, per mol of silver halide.

The compounds of the present invention can be used in the form of asolution dissolved in appropriate water-miscible organic solvents suchas alcohols (e.g., methanol, ethanol, propanol and fluorinatedalcohols), ketones (e.g., acetone and methyl ethyl ketone),dimethylformamide, dimethyl sulfoxide or methyl cellosolve.

Using a well-known emulsification and dispersion method, the compoundsof the present invention may also be dissolved in an oil such as dibutylphthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalateor in an auxiliary solvent such as ethyl acetate or cyclohexanone andthereafter the resulting solution may be formed into an emulsion bymechanical emulsification and dispersion. In addition, a known soliddispersion may be employed in which a powder of a compound of thepresent invention is dispersed in water by the use of a ball mill orcolloid mill or by imparting ultrasonic waves thereto.

The compound represented by the formula (1) or (2) of the presentinvention is added to a silver halide emulsion layer or otherhydrophilic colloid layer. If desired, it may be added to at least onelayer of plural silver halide emulsion layers. Some embodiments ofconstitution of layers of photographic materials to which the compoundsof the present invention are added are described below, but the presentinvention is not limited thereto.

Constitution (1)

A silver halide emulsion layer containing a compound of the presentinvention and a protective layer are formed on a support. The emulsionlayer or the protective layer may further contain an additionalhydrazine compound as a nucleating agent.

Constitution (2)

A first silver halide emulsion layer and a second silver halide emulsionlayer are formed on a support in order; and the first silver halideemulsion layer or an adjacent hydrophilic colloid layer contains anadditional hydrazine compound as a nucleating agent, and the secondsilver halide emulsion layer or an adjacent hydrophilic colloid layercontains a compound of the present invention.

Constitution (3)

The same as Constitution (2), except that the order of the two emulsionlayers is reversed.

In both Constitution (2) and Constitution (3), an interlayer containinga gelatin or a synthetic polymer (e.g., polyvinyl acetate and polyvinylalcohol) may be provided between the two light-sensitive emulsionlayers.

Constitution (4)

A silver halide emulsion layer containing an additional hydrazinecompound as a nucleating agent is formed on a support, and a hydrophiliccolloid layer containing a compound of the present invention is providedon the emulsion layer or between the support and the emulsion layer.

Especially preferred are Constitution (2) and Constitution (3).

Additional hydrazine compounds which can be employed in the presentinvention as a nucleating agent are preferably those represented by thefollowing formula (I): ##STR31## wherein R₁₁ represents an aliphaticgroup or an aromatic group; R₁₂ represents a hydrogen atom, an alkylgroup, an aryl group, an alkoxy group, an aryloxy group, an amino groupor a hydrazino group; G₁₁ represents ##STR32## a thiocarbonyl group oran iminomethylene group; A₁₁ and A₁₂ are both hydrogen atoms, or onerepresents a hydrogen atom, and the other represents a substituted orunsubstituted alkylsulfonyl group having from 1 to 10 carbon atoms,e.g., a methylsulfonyl group, or a substituted or unsubstitutedarylsulfonyl group having from 6 to 10 carbon atoms, e.g., aphenylsulfonyl group, or a substituted or unsubstituted acyl grouphaving from 2 to 10 carbon atoms, e.g., an acetyl group or a benzoylgroup; and R₁₃ is selected from the range as defined for R₁₂, and it maybe different from R₁₂.

In formula (I), the aliphatic group to be represented by R₁₁ ispreferably one having from 1 to 30 carbon atoms, and it is especiallypreferably a linear, branched or cyclic alkyl group having from 1 to 20carbon atoms. The alkyl group optionally may be substituted.

In formula (I), the aromatic group to be represented by R₁₁ is amonocyclic or bicyclic aryl or unsaturated heterocyclic group. Theunsaturated heterocyclic group may be condensed with an aryl group toform a condensed unsaturated heterocyclic group.

Preferably, R₁₁ is an aryl group; and especially preferably, it is anaryl group containing a benzene ring(s).

The aliphatic group or aromatic group to be represented by R₁₁optionally may be substituted. Typical examples of substituents for thegroup include an alkyl group, an aralkyl group, an alkenyl group, analkynyl group, an alkoxy group, an aryl group, a substituted aminogroup, a ureido group, a urethane group, an aryloxy group, a sulfamoylgroup, a carbamoyl group, an alkyl or arylthio group, an alkyl orarylsulfonyl group, an alkyl or arylsulfinyl group, a hydroxyl group, ahalogen atom, a cyano group, a sulfone group, an aryloxycarbonyl group,an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamidogroup, a sulfonamido group, a carboxyl group, a phosphorylamido group, adiacylamino group, an imido group, and ##STR33## (wherein R₁₄ and R₁₅may be selected from the range of R₂ and they may be different from eachother). Preferred are an alkyl group (preferably having from 1 to 20carbon atoms), an aralkyl group (preferably having from 7 to 30 carbonatoms), an alkoxy group (preferably having from 1 to. 20 carbon atoms),a substituted amino group (preferably one substituted by alkyl group(s)each having from 1 to 20 carbon atoms), an acylamino group (preferablyhaving from 2 to 30 carbon atoms), a sulfonamido group (preferablyhaving from 1 to 30 carbon atoms), a ureido group (preferably havingfrom 1 to 30 carbon atoms), and a phosphorylamido group (preferablyhaving from 1 to 30 carbon atoms). The groups may further besubstituted.

In formula (I), the alkyl group represented by R₁₂ is preferably onehaving from 1 to 4 carbon atoms; and the aryl group represented by thesame is preferably a monocyclic or bicyclic aryl group (for example,containing benzene ring(s)). The aryl group, the alkoxy group and thearyloxy group represented by R₁₂ are those having not more than 20carbon atoms, preferably not more than 15 carbon atoms and morepreferably not more than 10 carbon atoms.

Where G₁₁ is ##STR34## R₁₂ is preferably a hydrogen atom, an alkyl group(e.g., methyl, trifluoromethyl, 3-hydroxypropyl,3-methanesulfonamidopropyl and phenylsulfonylmethyl), an aralkyl group(e.g., o-hydroxybenzyl) or an aryl group (e.g., phenyl,3,5-dichlorophenyl, o-methanesulfonamidophenyl, 4-methanesulfonylphenyland 2-hydroxymethylphenyl), and it is especially preferably a hydrogenatom.

R₁₂ may optionally be substituted, and examples of substituents for thegroup R₁₂ include those for the above-described group R₁₁ ; .

In formula (I), G₁₁ is most preferably ##STR35##

R₁₂ may also be a group which has a function of cleaving the moiety ofG₁₁ -R₁₂ from the remaining molecule to cause cyclization forming acyclic structure containing the atoms of the moiety -G₁₁ -R₁₂. Examplesof such a group are, for example, those described in JP-A-63-29751.

A₁₁ and A₁₂ are most preferably hydrogen atoms.

In formula (I), R₁₁ or R₁₂ may contain therein a ballast group, which isordinarily used in passive (inactive) photographic additives such ascouplers, or a polymer residue. Such a ballast group is one having 8 ormore carbon atoms which is relatively inactive to photographicproperties, and may be selected, for example, from an alkyl group, analkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group andan alkylphenoxy group. Examples of polymers usable for the purpose arethose described in JP-A-1-100530.

In formula (I), R₁₁ or R₁₂ may contain therein a group having a functionof promoting adsorption of the compound of formula (I) to the surfacesof silver halide grains. Examples of such adsorbing promoting groupsinclude a thiourea group, a heterocyclic thioamido group, amercapto-heterocyclic group, a triazole group and others described inU.S. Pat. Nos. 4,385,108 and 4,459,347, and JP-A-59-195233,JP-A-59-200231, JP-A-59-201045, JP-A-59-201046, JP-A-59-201047,JP-A-59-201048, JP-A-59-201049, JP-A-61-170733, JP-A-61-270744,JP-A-62-948, JP-A-63-234244, JP-A-63-234245 and JP-A-62-234246.

Specific examples of compounds of formula (I) are shown below, but thepresent invention is not limited thereto. ##STR36##

Hydrazine compounds other than those described above, which are usefulin the present invention as a nucleating agent include the compoundsdescribed in Research Disclosure, Item 23516 (November, 1983) andliterature as referred to therein, as well as in U.S. Pat. Nos.4,080,207, 4,169,929, 4,276,364, 4,278,748, 4,385,108, 4,459,347,3,560,638 and 4,478,928, British Patent 2,011,391B, JP-A-60-179734,JP-A-62-270948, JP-A-63-29751, JP-A-61-1707333, JP-A-61-270744 andJP-A-62-270948, European Patents 217,310 and 356,898, U.S. Pat. No.4,686,167, JP-A-62-178246, JP-A-63-32538, JP-A-63-104047,JP-A-63-121838, JP-A-63-129337, JP-A-63-223744, JP-A-63-234244,JP-A-63-234245, JP-A-63-234246, JP-A-63-294552, JP-A-63-306438,JP-A-1-100530, JP-A-1-105941, JP-A-1-105943, JP-A-64-10233,JP-A-1-90439, JP-A-1-276128, JP-A- 1-280747, JP-A-1-283548,JP-A-1-283549, JP-A-1-285940, JP-A-63-147339, JP-A-63-179760,JP-A-63-229163, JP-A-2-198440, JP-A-2-198441, JP-A-2-198442,JP-A-2-196234, JP-A-2-196235, JP-A-2-220042, JP-A-2-221953,JP-A-2-221954, JP-A-2-302750 and JP-A-2-304550. Methods for preparingthe hydrazine compounds represented by formula (1) are also disclosed inthese references.

The amount of the hydrazine compound added to the photographic materialof the present invention as a nucleating agent is preferably from 1×10⁻⁶mol to 5×10⁻² mol, especially preferably from 1×10⁻⁵ mol to 2×10⁻² mol,per mol of silver halide.

For dissolution or dispersion of the nucleating hydrazine compound usedin the present invention, the same methods as those described above fordissolving or dispersing redox compounds of formula (1) or (2) may beemployed.

Any silver halide of silver chloride, silver bromide, silverchlorobromide, silver iodochloride or silver iodochlorobromide may beused for forming the photographic material of the present invention.

The silver halide grains for use in the present invention are preferablyfine grains (for example, having a mean grain size of 0.7 μm or less).Especially, the grains have a mean grain size of 0.5 μm or less. Thoughthe grain size distribution of the grains is basically not limitative,the grains are preferably in the form of a monodispersed emulsion. The"monodispersed emulsion" as referred to herein means that at least 95%by number or by weight of the silver halide grains in the emulsion havea grain size falling within the range of the mean grain size plus/minus40%.

The silver halide grains in the photographic emulsions constituting thephotographic material of the present invention may be regular crystals,such as cubic or octahedral crystals, may be irregular crystals, such asspherical or tabular crystals or composite crystals composed of suchvarious crystal forms.

The silver halide grains may have a uniform phase throughout the wholegrain or may have different phases in the inside of the grain and thesurface layer thereof. Two or more different silver halide emulsionsseparately prepared may be blended for use in the present invention.

The silver halide grains used for the photographic material of thepresent invention can be formed or physically ripened in the presence ofa cadmium salt, a sulfite, a lead salt, a thallium salt, a rhodium saltor a complex salt thereof, or an iridium salt or a complex salt thereof.

The emulsion layers and other hydrophilic colloid layers of thephotographic material of the present invention can contain variouswater-soluble dyes, as a filter dye, for the purpose of anti-irradiationor for other various purposes. As filter dyes, usable are dyes thatfurther lower photographic sensitivity, preferably ultravioletabsorbents having a color absorption maximum in the intrinsicsensitivity range of silver halides or dyes having a substantial lightabsorption essentially in the range of from 350 nm to 600 nm for thepurpose of elevating the safety to a safe light where the photographicmaterial is handled as a daylight material.

The dyes are added to the emulsion layers of the photographic material,or they are preferably added to and fixed in an upper layer over thesilver halide emulsion layers or a non-light-sensitive hydrophiliccolloid layer which is remote from the support with respect to thesilver halide emulsion layers, along with a mordant.

The amount of the dye to be added for the purpose may be generally from10⁻² g/m² to 1 g/m², preferably from 50 mg to 500 mg/m², though varyingin accordance with the molar extinction coefficient of the dye.

Specific examples of dyes usable in the present invention are describedin JP-A-63-64039, and preferred examples of dyes are shown below.##STR37##

The above dyes may be dissolved in an appropriate solvent (for example,water, alcohols such as methanol, ethanol or propanol, acetone, methylcellosolve, or a mixed solvent thereof), and the resulting solution maybe added to the non-light-sensitive hydrophilic colloid layer-coatingcomposition before preparing the photographic material of the presentinvention.

Two or more of the dyes may be used in combination.

The dyes may be incorporated into the photographic material of thepresent invention in such an amount that is sufficient for making thematerial processable under a daylight condition.

Concretely, the amount of the dye may be generally from 10⁻³ g/m² to 1g/m², especially preferably from 10⁻³ g/m² to 0.5 g/m².

As a binder or protective colloid for photographic emulsions of thephotographic material of the present invention, a gelatin is usedadvantageously, but any other hydrophilic colloids also may be used. Forinstance, usable are proteins such as gelatin derivatives, graftcopolymers of gelatin and other high polymers, albumin and casein;cellulose derivatives such as hydroxyethyl cellulose, carboxymethylcellulose and cellulose sulfates; saccharide derivatives such as sodiumalginate and starch derivatives; and other various synthetic hydrophilichigh polymer substances of homopolymers or copolymers such as polyvinylalcohol, polyvinyl partial acetal, poly-N-vinyl pyrrolidone, polyacrylicacid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole andpolyvinyl butyral.

As a gelatin, an acid-processed gelatin also may be used in addition toa lime-processed gelatin. Additionally, a gelatin hydrolysate and anenzyme-decomposed gelatin also may be used.

Silver halide emulsions used for the photographic material of thepresent invention may be or may not be chemically sensitized. The meansof chemical sensitization of silver halide emulsions can be known sulfursensitization technique, reduction sensitization and noble metalsensitization. Any may be employed singly or in combination of two ormore of them for the chemical sensitization of silver halide emulsionsfor use in the present invention.

Gold sensitization is a typical embodiment of noble metal sensitization,using a gold compound, essentially a gold complex. Complexes of anyother noble metals than gold, such as platinum, palladium or iridium,also may be used. Specific examples of usable noble metal complexes aredescribed in, for example, U.S. Pat. No. 2,448,060 and British Patent618,061.

Examples of sulfur sensitizing agents useful for sulfur sensitizationinclude sulfur compounds contained in gelatin, as well as other varioussulfur compounds such as thiosulfates, thioureas, thiazoles andrhodanines.

Examples of reduction sensitizing agents useful for reductionsensitization include stannous salts, amines, formamidinesulfinic acidsand silane compounds.

The silver halide emulsion layers of the photographic material of thepresent invention can contain known color sensitizing dyes.

The photographic material of the present invention can contain variouscompounds for preventing the materials from fogging during manufacture,storage or photographic processing thereof or for the purpose ofstabilizing the photographic properties of the material. For instance,various compounds which are known as an antifoggant or stabilizer can beemployed for the purpose and include azoles such as benzothiazoliumsalts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles,mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles,aminotriazoles, benzothiazoles and nitrobenzotriazoles;mercaptopyrimidines; mercapto triazines; thioketo compounds such asoxazolinethione; azaindenes such as triazaindenes, tetrazaindenes(especially, 4-hydroxy-substituted (1,3,3a,7)-tetrazaindenes),pentazaindenes; as well as benzenethiosulfonic acids, benzenesulfinicacids and benzenesulfonic acid amides. Above all, benzotriazoles (forexample, 5-methyl-benzotriazole) and nitroindazoles (for example,5-nitroindazole) are preferred. The compounds may be added to theprocessing solutions used for processing the photographic material.

The photographic material of the present invention can contain aninorganic or organic hardening agent in the photographic emulsion layersor other hydrophilic colloid layers. For instance, one or more selectedfrom chromium salts (e.g., chromium alum), aldehydes (e.g.,glutaraldehyde), N-methylol compounds (e.g., dimethylolurea), dioxanederivatives, active vinyl compounds (e.g.,1,3,5-triacryloyl-hexahydro-s-triazine and1,3-vinylsulfonyl-2-propanol), active halogen compounds (e.g.,2,4-dichloro-6-hydroxy-s-triazine) and mucohalogenic acids can be usedsingly or in combination for the purpose.

The photographic material of the present invention further can containvarious surfactants in the photographic emulsion layers or otherhydrophilic colloid layers for various purposes such as coatingassistance, prevention of static charge, improvement of slide property,emulsification and dispersion, prevention of surface blocking andimprovement of photographic characteristics (for example, accelerationof developability, elevation of contrast and enhancement ofsensitivity).

For instance, usable for the purpose are nonionic surfactants such assaponins (steroid type), alkylene oxide derivatives (e.g., polyethyleneglycol, polyethylene glycol/polypropylene glycol condensates,polyethylene glycol alkyl ethers, polyethylene glycol alkylaryl ethers,polyethylene glycol esters, polyethylene glycol sorbitan esters,polyalkylene glycol alkylamines, polyalkylene glycol alkylamides, andsilicone-polyethylene oxide adducts), glycidol derivatives (e.g.,alkenylsuccinic acid polyglycerides and alkylphenol polyglycerides),fatty acid esters of polyalcohols and alkyl esters of saccharides;anionic surfactants containing an acid group such as a carboxyl group, asulfo group, a phospho group, a sulfate group or a phosphate group, forexample, alkylcarboxylic acid salts, alkylsulfonic acid salts,alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts,alkylsulfate esters, alkylphosphate esters, N-acyl-N-alkyltaurins,sulfosuccinate esters, sulfoalkylpolyoxyethylene alkylphenyl ethers andpolyoxyethylene alkylphosphate esters; ampholytic surfactants such asamino acids, aminoalkylphosphonic acids, aminoalkyl sulfate, aminoalkylphosphate esters, alkylbetaines and amine oxides; and cationicsurfactants such as alkylamine salts, aliphatic or aromatic quaternaryammonium salts, heterocyclic quaternary ammonium salts (e.g., pyridiniumsalts and imidazolium salts) and aliphatic or heterocyclic phosphoniumor sulfonium salts.

Surfactants especially preferably used in the present invention arepolyalkylene oxides having a molecular weight of 600 or more, asdescribed in JP-B-58-9412. (The term "JP-B" as used herein means an"examined Japanese patent publication".) Additionally, it may furthercontain a polymer latex such as a polyalkyl acrylate, for improvement ofthe dimensional stability of the material.

For processing the photographic material of the present invention, thedeveloper used may contain a development accelerator or an acceleratorfor nucleating infectious development. As the accelerator, effective arecompounds described in JP-A-53-77616, JP-A-54-37732, JP-A-53-137133,JP-A-60-140340 and JP-A-60-14959, as well as other various compoundscontaining N and/or S atoms.

Specific examples of such compounds are shown below. ##STR38##

The optimum amount of the accelerator added to the photographic materialof the present invention is, though varying in accordance with the kindof the compound, desirably from 1.0×10⁻³ to 0.5 g/m², more preferablyfrom 5.0×10⁻³ to 0.1 g/m². The accelerator may be added to the coatingcompositions constituting the photographic material of the presentinvention, in the form of a solution dissolved in an appropriatesolvent, such as water, alcohols (e.g., methanol and ethanol), acetone,dimethylformamide or methyl cellosolve.

Plural kinds of additives may be used in combination.

For obtaining ultra-hard photographic images by processing thephotographic material of the present invention, known infectiousdevelopers or high-alkali developers having a pH value of about 13 asdescribed in U.S. Pat. No. 2,419,975 are unnecessary but any otherstable developers can be used.

Specifically, the silver halide photographic material of the presentinvention may well be processed with a developer containing a sulfiteion as a preservative in an amount of 0.10 mol/liter or more and havinga pH value of from 9.0 to 12.3, especially from 10.5 to 12.0, wherebysufficiently ultra-hard negative images can be obtained.

The developing agent in the developer used for processing thephotographic material of the present invention is not definedspecifically but various compounds as described in T.H. James, TheTheory of the Photographic Process, 4th Ed. (published by MacmillanCo.), pages 298 to 327 can be used.

For instance, dihydroxybenzenes (e.g., hydroquinone), 3-pyrazolidones(e.g., 1-phenyl-3-pyrazolidone and4,4-dimethyl-1-phenyl-3-pyrazolidone), aminophenols (e.g.,N-methyl-p-aminophenol), ascorbic acid and hydroxylamines can be usedsingly or in combination.

The silver halide photographic material of the present invention isdeveloped preferably with a developer containing a dihydroxybenzenecompound as a main developing agent and a 3-pyrazolidone or aminophenolcompound as an auxiliary developing agent. Desirably, in the developerof the type, the content of the dihydroxybenzene compound is from 0.05to 0.5 mol/liter and that of the pyrazolidone or aminophenol compound is0.06 mol/liter or less.

Amines may be added to the developer used for processing thephotographic material of the present invention for the purpose ofaccelerating the developing rate and shortening the development time,following the disclosure of U.S. Pat. No. 4,269,929.

The developer may further contain a pH buffer such as alkali metalsulfites, carbonates, borates or phosphates, as well as a developmentinhibitor or antifoggant such as iodides, bromides or organicantifoggants (especially preferably, nitroindazoles or benzotriazoles).Additionally, it may also contain, if desired, a water softener, adissolution aid, a toning agent, a development accelerator, a surfactant(especially preferably, the above-mentioned polyalkylene oxides), adefoaming agent, a hardening agent, and an inhibitor for silver stainson films (for example, silver 2-mercaptobenzimidazolesulfonate).

As a fixer used for processing the developed photographic material ofthe present invention, one having a conventional composition may beused. As the fixing agent, thiosulfates, thiocyanates as well as anyother organic sulfur compounds which are known to have an activity as afixing agent can be used. The fixer may contain a water-solublealuminium salt or the like as a hardening agent.

The processing temperature in processing the photographic material ofthe present invention generally can be from 18° C. to 50° C.

An automatic developing machine is preferably employed for processingthe photographic material of the present invention. The total processingtime of processing the material in an automatic developing machine,which indicates the time necessary from introduction of the material tobe processed into the machine to taking out of the finished materialfrom the machine, may be set to fall within the range of from 90 secondsto 120 seconds, whereupon an excellent image having a sufficientlyultra-hard negative gradation can be formed on the processed material.

The developer used for processing the photographic material of thepresent invention can contain compounds described in JP-A-56-24347 as asilver stain inhibitor. As a dissolution aid which may be added to thedeveloper, compounds described in JP-A-61-267759 can be employed. As apH buffer which may also be added to the developer, compounds describedin JP-A-60-93433 and compounds described in JP-A-62-186259 can beemployed.

When the photographic material of the present invention is a colorphotographic material, the material may comprise at least oneblue-sensitive silver halide emulsion layer, at least onegreen-sensitive silver halide emulsion layer and at least onered-sensitive silver halide emulsion layer on a support. In thematerial, the number of the silver halide emulsion layers andnon-light-sensitive layers as well as the order of the layers on thesupport is not limited specifically. A typical example is a silverhalide color photographic material having plural light-sensitive layerunits each composed of plural silver halide emulsion layers each havinga substantially same color sensitivity but having a differentsensitivity degree. The respective light-sensitive layers are unitlight-sensitive layers each having a color-sensitivity to any of bluelight, green light and red light. In such a multi-layer silver halidecolor photographic material, in general, the order of thelight-sensitive layer units on the support comprises a red-sensitivelayer unit, a green-sensitive layer unit and a blue-sensitive layer unitas formed on the support in that order. As the case may be, however, theorder may be opposite to the above-mentioned order, depending on theobject of the photographic material. As still another embodiment, adifferent color-sensitive layer may be sandwiched between other two andthe same color-sensitive layers.

Various non-light-sensitive layers such as an interlayer may be providedbetween the above-mentioned silver halide light-sensitive layers, or onor below the uppermost layer or lowermost layers.

Such an interlayer may contain various couplers and DIR compoundsdescribed in JP-A-61-43748, JP-A-59-113438, JP-A-59-113440,JP-A-61-20037 and JP-A-61-20038, and it may also contain conventionalcolor mixing preventing agents.

As the constitution of the plural silver halide emulsions of therespective light-sensitive layer units, preferred is a two-layeredconstitution composed of a high-sensitivity emulsion layer and alow-sensitivity emulsion layer as described in West German Patent1,121,470 and British Patent 923,045. In general, it is preferred thatthe plural light-sensitive layers are arranged on the support in such away that the sensitivity degree of the layer is to decrease gradually inthe direction to the support. In the embodiment, a non-light-sensitivelayer may be provided between the plural silver halide emulsion layers.As another embodiment, a low-sensitivity emulsion layer is formed remotefrom the support and a high-sensitivity emulsion layer is formed near tothe support, as described in JP-A-57-112751, JP-A-62-200350,JP-A-62-206541, and JP-A-62-206543.

Specific examples of the layer constitution on the support are mentionedan order of low-sensitivity blue-sensitive layer (BL)/high-sensitivityblue-sensitive layer (BH)/high-sensitivity green-sensitive layer(GH)/low-sensitivity green-sensitive layer (GL)/high-sensitivityred-sensitive layer (RH)/low-sensitivity red-sensitive layer (RL) fromthe remotest side from the support; an order of BH/BL/GL/GH/RH/RL; andan order of BH/BL/GH/GL/RL/RH.

Other examples are an order of blue-sensitive layer/GH/RH/GL/RL from theremotest side from the support, as described in JP-B-55-34932; and anorder of blue-sensitive layer/GL/RL/GH/RH from the remotest side fromthe support, as described in JP-A-56-25738 and JP-A-62-63936.

A further example is a three-layer unit as described in JP-B-49-15495,where the uppermost layer is a highest-sensitivity silver halideemulsion layer, the intermediate layer is a silver halide emulsion layerhaving a lower sensitivity than the uppermost layer and the lowermostlayer is a silver halide emulsion layer having a further lowersensitivity than the intermediate layer. That is, in the layerconstitution of the type, the sensitivity degree of each emulsion layeris lowered gradually to the direction of the support. Even in thethree-layer constitution of the type, each of the same color-sensitivitylayers may be composed of three layers of middle-sensitivity emulsionlayer/high-sensitivity emulsion layer/low-sensitivity emulsion layer asformed in that order from the remotest side from the support, as sodescribed in JP-A-59-202464.

Still other examples of the layer constitution of the photographicmaterial of the present invention are an order of high-sensitivityemulsion layer/low-sensitivity emulsion layer/middle-sensitivityemulsion layer and an order of low-sensitivity emulsionlayer/middle-sensitivity emulsion layer/high-sensitivity emulsion layer.

When the photographic material of the invention has four or more layers,the layer constitution thereof may be varied in accordance with themanner described above.

To improve color reproducibility, it is desired to provide a donor layer(CL) which has an interlayer effect and which has a different colorsensitivity distribution from that of the essential light-sensitivelayers of BL, GL and RL, adjacent to or near the essentiallight-sensitive layers, in the manner as described in U.S. Pat. Nos.4,705,744 and 4,707,436 and JP-A-62-160448 and JP-A-63-89850.

As described above, various layer constitutions and arrangements can beselected in accordance with the object of the photographic material ofthe invention.

When the photographic material of the present invention is a colornegative film or color reversal film, the silver halide preferably inthe photographic emulsion layer of the material is silver iodobromide,silver iodochloride or silver iodochlorobromide having a silver iodidecontent of about 30 mol % or less. Especially preferred is a silveriodobromide or silver iodochlorobromide having a silver iodide contentof from about 2 mol % to about 25 mol %.

Where the photographic material of the present invention is a colorphotographic paper, the silver halide contained in the photographicemulsion of the material is preferably silver chlorobromide or silverchloride which is substantially free from silver iodide. The silverhalide emulsion which is substantially free from silver iodide asreferred to herein means that the emulsion has a silver iodide contentof 1 mol % or less, preferably 0.2 mol % or less. The halogencomposition of such a silver chlorobromide emulsion may have any desiredproportion of silver bromide/silver chloride. The proportion may varywidely in accordance with the object, but preferably the proportion ofsilver chloride is 2 mol % or more. A so-called high silver chlorideemulsion having a high silver chloride content is used preferably inpreparing a photographic material suitable for rapid processing. Thesilver chloride content of such a high silver chloride emulsion ispreferably 90 mol % or more, especially preferably 95 mol % or more. Forthe purpose of reducing the amount of replenisher used in processing thephotographic material, an almost pure silver chloride emulsion having asilver chloride content of from 98 to 99.9 mol % also is usedpreferably.

The silver halide grains in the photographic emulsions of thephotographic material of the present invention may be regularcrystalline grains such as cubic, octahedral or tetradecahedral grains,irregular crystalline grains such as spherical or tabular grains,irregular crystalline grains having a crystal defect such as a twinplane or composite crystalline grains composed of the above-mentionedregular and irregular crystalline forms.

Regarding the grain size of the silver halide grains, the grains may befine grains having a small grain size of about 0.2 micron or less or maybe large grains having a large grain size of up to about 10 microns asthe diameter of the projected area. The emulsion of the grains may beeither a polydispersed emulsion or a monodispersed emulsion.

The silver halide photographic emulsions used in the present inventionmay be prepared by various methods, for example, those described inResearch Disclosure (RD) No. 17643 (December, 1978), pages 22 to 23 (I.Emulsion Preparation and Types); RD No. 18716 (November, 1979), pages648; P. Glafkides, Chimie et Physique Photographique (published by PaulMontel, 1967); G. F. Duffin, Photographic Emulsion Chemistry (publishedby Focal Press, 1966); and V. L. Zelikman et al, Making and CoatingPhotographic Emulsion (published by Focal Press, 1964).

Monodispersed emulsions as described in U.S. Pat. Nos. 3,574,628 and3,655,394 and British Patent 1,413,748 also are used preferably in thepresent invention.

Additionally, tabular grains having an aspect ratio of about 5 or morecan also be used in the present invention. Such tabular grains can beprepared easily in accordance with the various methods, for example, asdescribed in Gutoff, Photographic Science and Engineering, Vol. 14,pages 248 to 257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,430,048,4,439,520 and British Patent 2,112,157.

Regarding the crystal structure of the silver halide grains of theemulsions of the present invention, the grains may have the same halogencomposition throughout the whole grain, they may have different halogencompositions between the inside and the outside of one grain, or theymay have a layered structure. Further, the grains may have differenthalogen compositions as conjugated by epitaxial bond, or they may haveother components than silver halides, such as silver rhodanide or leadoxide, as conjugated with the silver halide matrix. Additionally, amixture of various grains of different crystalline forms may be employedin the present invention.

The emulsions for use in the present invention are generally physicallyripened, chemically ripened and/or color-sensitized. Additives used insuch a ripening or sensitizing step are described in Research DisclosureNos. 17643 and 18716, and the related descriptions in those referencesare shown in Table A below.

The photographic material of the present invention preferably containsnon-light-sensitive fine silver halide grains. Non-light-sensitive finesilver halide grains are meant to be fine silver halide grains which arenot sensitive to the light as imparted to the photographic material forimagewise exposure thereof and are substantially not developed in thestep of development of the exposed material. The fine grains aredesirably not fogged previously.

The fine silver halide grains have a silver bromide content of from 0 to100 mol % and, if desired, they may contain additionally silver chlorideand/or silver iodide. Preferably, they contain silver iodide in anamount of from 0.5 to 10 mol %.

The fine silver halide grains are desired to have a means grain size (asa mean value of the circle-corresponding diameter of the projected area)of from 0.01 to 0.5 μm, more preferably from 0.02 to 0.2 μm.

The fine silver halide grains may be prepared by the same method as thatof preparing ordinary light-sensitive silver halide grains. In the case,the surfaces of the fine silver halide grains do not need to beoptically sensitized and color sensitization of the grains isunnecessary. However, prior to adding the fine grains to the coatingcomposition, it is desirable to add previously a known stabilizer, suchas triazole compounds, azaindene compounds, benzothiazolium compounds,mercapto compounds or zinc compounds, to the coating composition.

Various known photographic additives which may be used in preparing thephotographic materials of the present invention are described in theabove-mentioned two Research Disclosures, and the related descriptionstherein are shown in the following table.

                  TABLE A                                                         ______________________________________                                        Kind of Additives                                                                             RD 17643   RD 18716                                           ______________________________________                                        1.   Chemical Sensitizer                                                                          p. 23      p. 648, right                                                                 column                                         2.   Sensitivity Enhancer      p. 648, right                                                                 column                                         3.   Spectral Sensitizer                                                                          pp. 23 to  p. 648, right                                       Supercolor Sensitizer                                                                        24         column to p. 649,                                                             right column                                   4.   Whitening Agent                                                                              p. 24                                                     5.   Anti-foggant   pp. 24 to  p. 649, right                                       Stabilizer     25         column                                         6.   Light-Absorbent                                                                              pp. 25 to  p. 649, right                                       Filter Dye     26         column to p. 650,                                   Ultraviolet Absorbent     left column                                    7.   Stain Inhibitor                                                                              p. 25,     p. 650, left to                                                    right      right column                                                       column                                                    8.   Color Image    p. 25                                                          Stabilizer                                                               9.   Hardening Agent                                                                              p. 26      p. 651, left                                                                  column                                         10.  Binder         p. 26      p. 651, left                                                                  column                                         11.  Plasticizer    p. 27      p. 650, right                                       Lubricant                 column                                         12.  Coating Aid    pp. 26 to  p. 650, right                                       Surfactant     27         column                                         13.  Antistatic Agent                                                                             p. 27      p. 650, right                                                                 column                                         ______________________________________                                    

In order to prevent deterioration of the photographic property of thephotographic material of the invention by formaldehyde gas as impartedthereto, compounds capable of reacting with formaldehyde so as tosolidify it, for example, those described in U.S. Pat. Nos. 4,411,987and 4,435,503, are preferably incorporated into the material.

Various color couplers can be incorporated into the photographicmaterial of the present invention, and examples of usable color couplersare described in patent publications as referred to in theabove-mentioned RD No. 17643, VII-C to G.

As yellow couplers, for example, those described in U.S. Pat. Nos.3,933,501, 4,022,620, 4,326,024, 4,401,752 and 4,248,961, JP-B-58-10739,British Patents 1,425,020 and 1,476,760, U.S. Pat. Nos. 3,973,968,4,314,023 and 4,511,649, and European Patent 249,473A are preferred.

As magenta couplers, 5-pyrazolone compounds and pyrazoloazole compoundsare preferred. For instance, those described in U.S. Pat. Nos. 4,310,619and 4,351,897, European Patent 73,636, U.S. Pat. Nos. 3,061,432 and3,725,045, RD No. 24220 (June, 1984), JP-A-60-33552, RD No. 24230 (June,1984), JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034 andJP-A-60-185951, U.S. Pat. Nos. 4,500,630, 4,540,654 and 4,556,630, andWO(PCT)88/04795 are preferred.

As cyan couplers, phenol couplers and naphthol couplers are preferred.For instance, those described in U.S. Pat. Nos. 4,052,212, 4,146,396,4,228,122, 4,296,200, 2,369,929, 2,801,171, 2,771,162,2,895,816,3,772,002, 3,758,308, 4,334,011 and 4,327,173, West German Patent (OLS)No. 3,329,729, European Patents 121,365A and 249,453A, U.S. Pat. Nos.3,446,622, 4,333,999, 4,753,871, 4,451,559, 4,427,767, 4.690,889,4,254,212 and 4,296,199, and JP-A-61-42658 are preferred.

As colored couplers for correcting the unnecessary absorption of coloreddyes, those described in RD No. 17643, U.S. Pat. No. 4,163,670,JP-B-57-39413, U.S. Pat. Nos. 4,004,929 and 4,138,258, and BritishPatent 1,146,368 are preferred. Additionally, couplers for correctingthe unnecessary absorption of the colored dye by the phosphor dye to bereleased during coupling, as described in U.S. Pat. No. 4,774,181, aswell as couplers having a dye precursor group capable of reacting with adeveloping agent to form dyes, as a split-off group, as described inU.S. Pat. No. 4,777,120 also are used preferably.

Couplers capable of forming colored dyes having a pertinentdiffusibility may also be used, and those described in U.S. Pat. No.4,366,237 British Patent 2,125,570, European Patent 96,570, and WestGerman Patent OLS No. 3,234,533 are preferred.

Polymerized dye-forming couplers also may be used, and typical examplesof such couplers are described in U.S Pat. Nos. 3,451,820, 4,080,211,4,367,282, 4,409,320 and 4,576,910, and British Patent 2,102,137.

Couplers capable of releasing a photographically useful residue alongwith coupling also may be used in the present invention. For instance,as DIR couplers releasing a development inhibitor, those described inthe patent publications as referred to in the above-mentioned RD No.17643, Item VII-F, as well as those described in JP-A-57-151944,JP-A-57-154234, JP-A-60-184248, JP-A-63-37346 and JP-A-63-37350 and U.S.Pat. Nos. 4,248,962 and 4,7782,012 are preferred.

As couplers that imagewise release a nucleating agent of developmentaccelerator during development, those described in British Patents2,097,140 and 2,131,188, JP-A-59-157638 and JP-A-59-170840 arepreferred.

Additionally, examples of compounds which may be incorporated into thephotographic materials of the present invention are competing couplersdescribed in U.S. Pat. No. 4,130,427; polyvalent couplers described inU.S. Pat. Nos. 4,238,472, 4,338,393 and 4,310,618; DIR redoxcompound-releasing couplers, DIR coupler-releasing couplers, DIRcoupler-releasing redox compounds and DIR redox-releasing redoxcompounds described in JP-A-60-185950 and JP-A-62-24252; couplersreleasing a dye which recolors after released from the coupler asdescribed in European Patents 173,302A and 313,308A; bleachingaccelerator-releasing couplers as described in RD Nos. 11449 and 24241,and JP-A-61-201247; ligand-releasing couplers described in U.S. Pat. No.4,553,477; leuco dye-releasing couplers described in JP-A-63-75747; andcouplers releasing a phosphor dye as described in U.S. Pat. No.4,774,181.

The above-mentioned couplers can be incorporated into the photographicmaterials of the present invention by various known dispersion methods.

For instance, an oil-in-water dispersion method may be employed for thepurpose. Examples of high boiling point solvents usable in the methodare described in U.S. Pat. No. 2,322,027.

Examples of high boiling point organic solvents having a boiling pointof 175° C. or higher at atmospheric pressure, which are used in anoil-in-water dispersion are phthalates (e.g., dibutyl phthalate,dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate,bis(2,4-di-t-amylphenyl) phthalate, bis(2,4-di-t-amylphenyl)isophthalate and bis(1,1-diethylpropyl) phthalate), phosphates orphosphonates (e.g., triphenyl phosphate, tricresyl phosphate,2-ethylhexyl diphenylphosphate, tricyclohexyl phosphate,tri-2-ethylhexyl phosphate, tridocyl phosphate, tributoxyethylphosphate, trichloropropyl phosphate and di-2-ethylhexylphenylphosphonate), benzoates (e.g., 2-ethylhexy benzoate, dodecyl benzoateand 2-ethylhexyl p-hydroxybenzoate), amides (e.g.,N,N-diethyldodecanamide, N,N-diethyllaurylamide andN-tetradecylpyrrolidone), alcohols or phenols (e.g., isostearyl alcoholand 2,4-di-tert-amylphenol), aliphatic carboxylates (e.g.,bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributylate,isostearyl lactate and trioctyl citrate), aniline derivatives (e.g.,N,N-dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (e.g.,paraffin, dodecylbenzene and diisopropylnaphthalene). As an auxiliarysolvent, organic solvents having a boiling point of approximately from30 to 160° C., preferably from 50 to 160° C. can be used. Examples ofsuch auxiliary organic solvents are ethyl acetate, butyl acetate, ethylpropionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetateand dimethylformamide.

A latex dispersion method also may be employed for incorporatingcouplers into the photographic material of the present invention. Thesteps of carrying out the dispersion method, the effect of the methodand examples of latexes usable in the method for impregnation aredescribed in U.S. Pat. No. 4,199,363, and West German Patent (OLS) Nos.2,541,174 and 2,541,130.

If desired, such a coupler is infiltrated into a loadable latex polymer(for example, as described in U.S. Pat. No. 4,203,716) in the presenceor absence of the above-mentioned high boiling point organic solvent oris dissolved in a water-insoluble and organic solvent-soluble polymerand is thereafter dispersed in an aqueous hydrophilic colloid solutionby emulsification.

Preferably, homopolymers or copolymers as described in InternationalPatent Application Laid-Open No. WO 88/00723, pages 12 to 20 are usedfor the purpose. In particular, acrylamide polymers are especiallypreferred in view of stabilization of the color images formed.

The color photographic material of the present invention preferablycontains an antiseptic of fungicide of various kinds, for example,selected from those described in JP-A-63-257747, 62-2722248 and 1-80941,such as 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol,4-chloro-3,5-dimethylphenol, 2-phenoxyethanol or2-(4-thiazolyl)benzimidazole.

The present invention may apply to various color photographic materials,Typical examples of such materials include color negative films forgeneral use or for movie use, as well as color papers, color positivefilms and color reversal papers.

Suitable supports which are usable in the present invention aredescribed in, for example, the above-mentioned RD No. 17643, page 28,and RD No. 18716, from page 647, right column to page 648, left column.

It is preferred that the total film thickness of all the hydrophiliccolloid layers provided on the surface of the support of having emulsionlayers is 28 μm or less, preferably 23 μm or less, more preferably 18 μmor less, especially preferably 16 μm or less, in the photographicmaterial of the present invention. It is also preferred that thephotographic material of the present invention has a film swelling rate(T 1/2) of 30 second or less, preferably 20 seconds or less. The filmthickness as referred to herein is one as measured under the controlledcondition of a temperature of 25° C. and a relative humidity of 55% (for2 days); and the film swelling rate as referred to herein may bemeasured by any means in the field. For instance, it may be measured bythe use of a swellometer of the model as described in A. Green et al.,Photographic Science Engineering, Vol. 19, No. 2, pages 124 to 129. Thefilm swelling rate (T 1/2) is defined as follows: 90% of the maximumswollen thickness of the photographic material as processed in a colordeveloper under the condition of 30° C. and 3 minutes and 15 seconds iscalled a saturated swollen thickness. The time necessary for attaining ahalf (1/2) of the saturated swollen thickness is defined to be a filmswelling rate (T 1/2).

The film swelling rate (T 1/2) can be adjusted by adding a hardeningagent to gelatin as a binder or by varying the condition of storing thecoated photographic material. Additionally, the photographic material ofthe present invention is desired to have a swelling degree of from 150to 400%. The swelling degree as referred to herein is calculated fromthe maximum swollen film thickness as obtained under the above-mentionedcondition, on the basis of a formula of:

    (maximum swollen film thickness-original film thickness)/(original film thickness).

The color photographic material of the present invention can bedeveloped by any ordinary method, for example, in accordance with theprocess described in the above-mentioned RD No. 17643, pages 28 and 29,and RD No. 18716, page 615, from left column to right column.

The color developer used for development of the photographic material ofthe present invention is preferably an aqueous alkaline solutionconsisting essentially of an aromatic primary amine color-developingagent. As the color-developing agent, p-phenylenediamine compounds arepreferably used, though aminophenol compounds are also useful. Specificexamples of p-phenylenediamine compounds usable as the color-developingagent include 3-methyl-4-amino-N,N-diethylaniline,3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline,3-methyl-4-amino-N-ethyl-N-β-methanesulfoneamidoethylaniline and3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, as well as sulfates,hydrochlorides and p-toluenesulfonates of the compounds. Above all,3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is especiallypreferred. The compounds can be used in combination of two or more, inaccordance with the object.

The color developer generally contains a pH buffer such as alkali metalcarbonates, borates or phosphates, and a development inhibitor oranti-foggant such as bromides, iodides, benzimidazoles, benzothiazolesor mercapto compounds. If desired, it may also contain variouspreservatives such as hydroxylamine, diethylhydroxylamine, sulfites,hydrazines such as N,N-biscarboxymethylhydrazine, phenylsemicarbazides,triethanolamine and catechol-sulfonic acids; an organic solvent such asethylene glycol and diethylene glycol; a development accelerator such asbenzyl alcohol, polyethylene glycol, quaternary ammonium salts andamines; a dye-forming coupler; a competing coupler; an auxiliarydeveloping agent such as 1-phenyl-3-pyrazolidone; a tackifier; as wellas various chelating agents such as aminopolycarboxylic acids,aminopolyphosphonic acids, alkylphosphonic acids and phosphonocarboxylicacids. Specific examples of chelating agents which may be incorporatedinto the color developer are ethylenediamine-tetraacetic acid,nitrilo-triacetic acid, diethylenetriamine-pentaacetic acid,cyclohexanediaminetetraacetic acid, hydroxylethyliminodiacetic acid,1-hydroxyethylidene-1,1-diphosphonic acid,nitrilo-N,N,N-trimethylenephosphonic acid,ethylenediamine-N,N,N,N-tetramethylenephosphonic acid,ethylenediaminedi(o-hydroxyphenylacetic acid) and their salts.

Where the photographic material is processed for reversal finish, ingeneral, it is first subjected to black-and-white development and thensubjected to color development. For the first black-and-whitedevelopment, a black-and-white developer which contains a conventionalblack-and-white developing agent, for example, dihydroxybenzenes such ashydroquinone, 3-pyraozlidones such as 1-phenyl-3-pyraozlidone, oraminophenols such as N-methyl-p-aminophenol, singly or in combination ofthem, is used.

The color developer and the black-and-white developer generally have apH value of from 9 to 12. The amount of the replenisher to the developeris, though depending upon the color photographic material to beprocessed, generally 3 liters or less per m² of the material to beprocessed. It may be reduced to 500 ml or less per m² of the material tobe processed by lowering the bromide ion concentration in thereplenisher. Where the amount of the replenisher is reduced, it ispreferred to reduce the contact area of the surface of the processingsolution in the processing tank with air so as to prevent vaporizationand air oxidation of the solution.

The contact surface area of the processing solution with air in theprocessing tank is represented by the opening ratio which is defined bythe following formula: ##EQU1##

The above-described opening ratio is preferably 0.1 or less, morepreferably from 0.001 to 0.05. Various means can be employed for thepurpose of reducing the opening ratio, which include, for example,provision of a masking substance such as a floating lid on the surfaceof the processing solution in the processing tank, employment of themobile lid described in JP-A-1-82033 and employment of theslit-developing method described in JP-A-63-216050. Reduction of theopening ratio is preferably applied to not only both steps of colordevelopment and black-and-white development but also all the subsequentsteps such as bleaching, bleach-fixation, fixation, rinsing andstabilization steps. In addition, the amount of the replenisher addedmay also be reduced by means of suppressing accumulation of bromide ionsin the developer.

The time for color development is generally within the range of from 2minutes to 5 minutes, but the processing time may be shortened byelevating the processing temperature, elevating the pH value of theprocessing solution and elevating the concentration of the processingsolution.

After color development, the photographic emulsion layer is generallybleached. Bleaching may be effected simultaneously with fixation(bleach-fixation) or separately therefrom. In order to accelerateprocessing speed, a system of bleaching followed by bleach-fixation mayalso be employed. If desired, a system of using a bleach-fixing bath oftwo continuous tanks, a system of fixation followed by bleach-fixation,or a system of bleach-fixation followed by bleaching may also beemployed, in accordance with the object. The bleaching agent can be, forexample, compounds of polyvalent metals such as iron(III), as well asperacids, quinones and nitro compounds. Specific examples of thebleaching agent usable in the present invention include organiccomplexes of iron(III), such as complexes thereof withaminopolycarboxylic acids such as ethylenediaminetetraacetic acid,diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid,methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid or glycolether-diaminetetraacetic acid or with organic acids such as citric acid,tartaric acid or malic acid. Aminopolycarboxylato/iron(III) complexessuch as ethylenediaminetetraacetato/iron(III) complex and1,3-diaminopropanetetraacetato/iron)(III) complex are preferred in viewof the rapid processability thereof and prevention of environmentalpollution. The aminopolycarboxylato/iron(III) complexes are especiallyuseful both in a bleaching solution and in a bleach-fixing solution. Thebleaching solution or bleach-fixing solution containing suchaminopolycarboxylato/iron(III) complexes generally has a pH value offrom 4.0 to 8, but the solution may have a lower pH value for rapidprocessing.

The bleaching solution, the bleach-fixing solution and the previous bathmay contain a bleaching accelerating agent, if desired. Variousbleaching accelerating agents are known, and examples of the agentswhich are used advantageously in the present invention include mercaptogroup- or disulfide group-containing compounds described in U.S. Pat.No. 3,893,858, German Patents 1,290,812 and 2,059,988, JP-A-53-32736,JP-A-53-57831, JP-A-53-37418, JP-A-53-72623, JP-A-53-95630,JP-A-53-95631, JP-A-53-104232, JP-A-53-124424, JP-A-53-141623 andJP-A-53-28426, RD No. 17129 (July, 1978); thiazolidine derivatives asdescribed in JP-A-50-140129; thiourea derivatives as described inJP-B-45-8506, JP-A-52-20832 and JP-A-53-32735 and U.S. Pat. No.3,706,561; iodide salts as described in German Patent 1,127,715 andJP-A-58-16235; polyoxyethylene compounds as described in German Patents966,410 and 2,748,430; polyamine compounds as described in JP-B-45-8836;other compounds as described in JP-A-49-40943, JP-A-49-59644,JP-A-53-94927, JP-A-54-35727, JP-A-55-26506 and JP-A-58-163940; andbromide ions. Above all, mercapto group- or disulfide group-containingcompounds, in particular, those as described in U.S. Pat. No. 3,893,858,German Patent 1,290,812 and JP-A-53-95630 are preferred, as having alarge accelerating effect. In addition, compounds described in U.S. Pat.No. 4,552,834 are also preferred. The bleaching accelerators may beincorporated into the photographic material of the invention. Where thematerial of the invention is a picture-taking color photographicmaterial and it is bleach-fixed, the bleaching accelerators areespecially effective.

The bleaching solution and bleach-fixing solution may further contain,in addition to the above-mentioned components, various organic acids forthe purpose of preventing bleaching stains. Especially preferred organicacids for the purpose are those having an acid dissociating constant(pKa) of from 2 to 5. For instance, acetic acid, propionic acid andhydroxyacetic acid are preferably used.

As the fixing agent in the fixing solution or bleach-fixing solutionapplied to the photographic material of the invention, usable arethiosulfates, thiocyanates, thioether compounds, thioureas, and a largeamount of iodide salts. Use of thiosulfates is general for the purpose.Above all, ammonium thiosulfate is used most widely. Additionally, acombination of thiosulfates and thiocyanates, thioether compounds orthioureas is also preferred. As the preservative in the fixing solutionor bleach-fixing solution, preferred are sulfites, bisulfites andcarbonyl-bisulfite adducts, as well as sulfinic acid compounds asdescribed in European Patent 294769A. Further, the fixing solution ofbleach-fixing solution may preferably contain variousaminopolycarboxylic acids or organic phosphonic acids for the purpose ofstabilizing the solution.

The total time for the desilvering process is preferably shorter withinthe range of not causing desilvering insufficiency. For instance, thetime is preferably from 1 minute to 3 minutes, more preferably from 1minute to 2 minutes. The processing temperature may be from 25° C. to50° C., preferably from 35° C. to 45° C. In such a preferred temperaturerange, the desilvering speed is accelerated and generation of stains inthe processed material may be prevented effectively.

In the delivering process, it is desired that stirring of the processingsolution during the process is promoted as much as possible. Examples ofreinforced stirring means for forcedly stirring the photographicmaterial during the desilvering step are a method of running a jetstream of the processing solution to the emulsion-coated surface of thematerial, as described in JP-A-62-183460; a method of promoting thestirring effect by the use of a rotating means, as described inJP-A-62-183461; a method of moving the photographic material beingprocessed in the processing bath while the emulsion-coated surface ofthe material is brought into contact with a wiper blade as provided inthe processing bath, whereby the processing solution as applied to theemulsion-coated surface of the material is made turbulent and thestirring effect is promoted; and a method of increasing the totalcirculating amount of the processing solution. Such reinforced stirringmeans are effective to any of the bleaching solution, bleach-fixingsolution and fixing solution. It is considered that reinforcement ofstirring of the processing solution would promote penetration of thebleaching agent and fixing agent into the emulsion layer of thephotographic material being processed and, as a result, the desilveringrate in processing the material would be elevated. The above-mentionedreinforced stirring means is more effective, when a bleachingaccelerator is incorporated into the processing solution. Because of themeans, therefore, the bleaching accelerating effect could be augmentedremarkably, and the fixation preventing effect by the bleachingaccelerator could be avoided.

The photographic material of the present invention can be processed withan automatic developing machine. It is desired that the automaticdeveloping machine used for processing the material of the presentinvention is equipped with a photographic material-conveying means asdescribed in JP-A-60-191257, JP-A-60-191258 and JP-A-60-191259. As isnoted from the related disclosure of JP-A-60-191257, the conveying meansmay noticeably reduce the carry-over amount from the previous bath tothe subsequent bath and therefore it is extremely effective forpreventing deterioration of the processing solution being used. Becauseof the reasons, the conveying means is especially effective forshortening the processing time in each processing step and for reducingthe amount of the replenisher to each processing bath.

The silver halide color photographic material of the present inventionis generally rinsed in water and/or stabilized, after being delivered.The amount of the water used in the rinsing step can be set in a broadrange, in accordance with the characteristic of the photographicmaterial being processed (for example, depending upon the raw materialcomponents, such as the coupler and so on) or the use of the material,as well as the temperature of the rinsing water, the number of therinsing tanks (the number of the rinsing stages), the replenishmentsystem of normal current or countercurrent and other various kinds ofconditions. Among the conditions, the relation between the number of therinsing tanks and the amount of the rinsing water in a multi-stagecountercurrent rinsing system can be obtained by the method described inJournal of the Society of Motion Picture and Television Engineers, Vol.64, pages 248 to 253 (May, 1955).

According to the multistage countercurrent system described in theabove-mentioned reference, the amount of the rinsing water used can bereduced noticeably, but because of the prolongation of the residencetime of the water in the rinsing tank, bacteria would propagate in thetank so that the floating substances generated by the propagation ofbacteria would adhere to the surface of the material as it wasprocessed. Accordingly, the above system would often have a problem. Inthe practice of processing the photographic material of the presentinvention, the method of reducing calcium and magnesium ions, which isdescribed in JP-A-62-288838, can be effectively used for overcoming theproblem. In addition, isothiazolone compounds and thiabendazolesdescribed in JP-A-57-8542; chlorine-containing bactericides such aschlorinated sodium isocyanurates; and benzotriazoles and otherbactericides described in H. Horiguchi, Chemistry of Bactericidal andFungicidal Agents (1986, by Sankyl Publishing Co., Japan), Bactericidaland Fungicidal Techniques to Microorganisms, edited by Association ofSanitary Technique, Japan (1982, by Kogyl Gijutsu-kai, Japan), andEncyclopeadia of Bactericidal and Fungicidal Agents, edited by NipponBactericide and Fungicide Association, Japan (1986), can also be used.

The ph value of the rinsing water used for processing the photographicmaterial of the present invention is from 4 to 9, preferably form 5 to8. The temperature of the rinsing water and the rinsing time can also beset variously in accordance with the characteristics of the photographicmaterial being processed as well as the use thereof, and in general, thetemperature is from 15 to 45° C. and the time is from 20 seconds to 10minutes, and preferably the temperature is from 25 to 40° C. and thetime is from 30 seconds to 5 minutes. Alternatively, the photographicmaterial of the present invention may also be processed directly with astabilizing solution in place of being rinsed with water. For thestabilization, any known methods, for example, as described inJP-A-57-8543, JP-A-58-14834 and JP-A-60-2203456, can be employed.

In addition, the material can also be stabilized following the rinsingstep. One example is a stabilizing bath containing a dye stabilizer anda surfactant, which is used as a final bath for picture-taking colorphotographic materials. Examples of dye stabilizers usable for thepurpose are aldehydes such as formalin and glutaraldehyde, N-methylolcompounds, hexamethylenetetramine and aldehyde-sulfite adducts.

The stabilizing bath may also contain various chelating agents andfungicides.

The overflow from the rinsing and/or stabilizing solutions because ofaddition of replenishers thereto may be re-used in the other steps suchas the previous desilvering steps.

Where the photographic material of the present invention is processedwith an automatic developing machine system and the processing solutionsused in the step are evaporated and thickened, it is desired to addwater to the solutions so as to correct the concentration of thesolutions.

The silver halide color photographic material of the present inventioncan contain a color developing agent for the purpose of simplifying andaccelerating the processing of the material. For incorporation of acolor developing agent into the photographic material, variousprecursors of the agent are preferably used. For example, indoanilinecompounds described in U.S. Pat. No. 3,342,597, Schiff base compoundsdescribed in U.S. Pat. No. 3,342,599 and RD Nos. 14850 and 15159, aldolecompounds described in RD No. 13924, metal complexes described in U.S.Pat. No. 3,719,492 and urethane compounds described in JP-A-53-135628can be used as precursors.

The silver halide color photographic material of the present inventioncan contain various kinds of 1-phenyl-3-pyrazolidones, if desired, forthe purpose of accelerating the color developability thereof. Specificexamples of these compounds are described in JP-A-56-64339,JP-A-57-144547 and JP-A-58-115438.

The processing solutions for the photographic material of the inventionare used at 10° C. to 50° C. In general, a processing temperature offrom 33° C. to 38° C. is standard, but the temperature may be madehigher so as to accelerate the processing or to shorten the processingtime, or on the contrary, the temperature may be made lower so as toimprove the quality of images formed and to improve the stability of theprocessing solution used.

The compounds of the present invention are also usable inheat-developing photographic materials. Details of heat-developingphotographic materials are described in, for example, U.S. Pat. Nos.4,463,079, 4,474,867, 4,478,927, 4,507,380, 4,500,626 and 4,483,914,JP-A-58-149046, JP-A-58-149047, JP-A-59-152440, JP-A-59-154445,JP-A-59-165054, JP-A-59-180548, JP-A-59-168439, JP-A-59-174832,JP-A-59-174833, JP-A-59-174834, JP-A-59-174835, JP-A-61-232451,JP-A-62-65038, JP-A-62-253159, JP-A-63-316848 and JP-A-64-13546, andEuropean Patent Publication Nos. 210,660A2 and 220,746A2.

The known heat-developing photographic materials basically havelight-sensitive silver halides, binders, dye-providing compoundsreducing agents (as the case maybe, dye-providing substances may actalso as a reducing agent) on a support and, if desired, they may containother additives such as organic silver salts.

The heat-developing photographic material of the type may be either oneto form a negative image by exposure or one to form a positive image byexposure. The latter case of forming a positive image may be either onecontaining a direct positive emulsion as a silver halide emulsion (whichmay be either in the form of a nucleating agent-containing system or inthe form of a fogged system) or one containing a dye-providing compoundcapable of releasing a positive diffusive dye image.

There are known various systems of transferring a diffusive dye, whichare, for example, a system of transferring a dye onto a dye-fixing layerby means of an image-forming solvent such as water, a system oftransferring dye onto a dye-fixing layer by means of a high boilingpoint organic solvent, a system of transferring a dye onto a dye-fixinglayer by means of a hydrophilic hot-melting solvent, and a system oftransferring a diffusive dye onto a dye-fixing layer having adye-receiving polymer by the action of the thermal diffusibility orsublimiability of the dye. Any one of such systems may be employed inthe present invention.

As the above-described image-forming solvent, water is known, which isnot limited to only a pure water but includes any and every conventionalwater. In addition, a mixed solvent comprising a pure water and a lowboiling point solvent such as methanol, dimethylformamide (DMF), acetoneor diisobutyl ketone may also be employed. Further, the solvent may alsobe in the form of a solution containing an image formation accelerator,an anti-foggant, a development stopper and a hydrophilic hot-meltingsolvent.

The present invention is described in more detail by way of thefollowing examples, which, however, are not intended to limit the scopeof the present invention.

EXAMPLE 1 Preparation of First Light-Sensitive Emulsion Layer

An aqueous 0.13 M silver nitrate solution and an aqueous halide solutioncontaining 1×10⁻⁷ mol per mol of silver of (NH₄)₃ RhCl₆, 2×10⁷ mol permol of silver of K₃ IrCl₆, 0.04 M of potassium bromide and 0.09 M ofsodium chloride were added to an aqueous gelatin solution containingsodium chloride and 1,3-dimethyl-2-imidazolidinethione, with stirring at38° C. over a period of 12 minutes by a double-jet method, to effectnucleation of obtaining silver chlorobromide grains having a mean grainsize of 0.15 μm and a silver chloride content of 70 mol %. Subsequently,an aqueous 0.87 M silver nitrate solution and an aqueous halide solutioncontaining 0.26 M of potassium bromide and 0.65 M of sodium chloridewere added thereto in the same manner by a double-jet method over aperiod of 20 minutes. Next, 1×10⁻³ mol of a KI solution was addedthereto for effecting conversion, and the resulting emulsion was washedwith water by means of a conventional flocculation method. 40 g ofgelatin was added to the thus washed emulsion which was then adjusted tohave a pH of 6.5 and a pAg of 7.5. Further, 5 mg of sodium thiosulfateper mol of silver and 8 mg of chloroauric acid per mol of silver wereadded to the emulsion, which was then heated at 60° C. for 60 minutesfor effecting chemical sensitization. 150 mg of 1,3,3a,7-tetrazaindenewas added thereto as a stabilizer. The grains thus formed were cubicsilver chlorobromide grains having a mean grain size of 0.28 μm and asilver chloride content of 70 mol %. (The fluctuation coefficient was10%.) The emulsion thus prepared was divided into plural parts. 1×10⁻³mol of5-[3-(4-sulfobutyl)-5chloro-2-oxazolidylidene]-1hydroxyethyl-3-(2-pyridyl)-2-thiohydantoinper mol of silver was added thereto as a sensitizing dye, and 2×10⁻⁴ molof 1-phenyl-5mercaptotetrazole per mole of silver, 5×10⁻⁴ mol per mol ofsilver of a short-wave cyanine dye having the following structuralformula (a), 200 mg/m² of a polymer of the following formula (b), 200mg/m² of a dispersion of polyethyl acrylate, 200 mg/m² of1,3-divinyl-sulfonyl-2-propanol as a hardening agent, and 2.8×10⁵ mol/m²of a hydrazine compound of the following formula (c) as a nucleatingagent were added thereto.

The resulting emulsion was coated on a polyethylene terephthalatesupport having a thickness of 100 μm having provided thereon a subbinglayer, in an amount of 3.6 g/m² as a silver coverage. ##STR39##

Coating of Interlayer

An interlayer comprising the following composition was coated over thefirst light-sensitive emulsion layer.

    ______________________________________                                        gelatin                 1.0 g/m.sup.2                                         1,3-bisvinylsulfonyl-2-propanol                                                                       4.0 wt. %                                                                     to gelatin                                            ______________________________________                                    

Preparation of Second Light-Sensitive Emulsion Layer Preparation ofLight-Sensitive Emulsion (B)

An aqueous silver nitrate solution and an aqueous solution containingpotassium iodide and potassium bromide were added simultaneously to anaqueous gelatin solution kept at 50° C., in the presence of 4×10⁻⁷ molof potassium iridium(III) hexachloride per mol of silver and ammonia,over a period of 60 minutes, which keeping the pAg value of the reactionsystem at 7.8 to prepare a cubic monodispersed emulsion having a meangrain size of 0.28 μm and a means silver iodide content of 0.3 mol %.The emulsion was desalted by means of a flocculation method, and then 40g of an inert gelatin per mol of silver was added thereto. Then, theemulsion was kept at 50° C. and then added to a mixture comprising asensitizing dye of5,5'-dichloro-9-ethyl-3,3'-bis(3-sulfopropyl)oxacarbocyanine and 10⁻³mol of a KI solution per mol of silver, and the resulting mixture waskept as it was for 15 minutes and then cooled. Thus, a light-sensitiveemulsion (B) was prepared.

Coating of Second Light-Sensitive Emulsion Layer

The light-sensitive emulsion (B) prepared above was re-dissolved, andthe following chemicals were added thereto at 40° C. The resultingcomposition was then coated over the interlayer in an amount of 0.4 g/m²as silver and 0.5 g/m² as gelatin.

    ______________________________________                                        5-Methylbenzotriazole 5.0 × 10.sup.-3                                                         mol/mol of Ag                                           6-Methyl-4-hydroxy-1,3,3a,7-                                                                          2 × 10.sup.-3                                   tetrazaindene         mol/mol of Ag                                           Polyethyl Acrylate     30 wt. %                                                                     to gelatin                                              1,3-Bisvinylsulfonyl-2-propanol                                                                     4.0 wt. %                                                                     to gelatin                                              Redox compound (shown in Table 1)                                                                   2.0 × 10.sup.-5                                                         mol/m.sup.2                                             ______________________________________                                    

Coating of Protective Layer

Over a second light-sensitive emulsion layer was coated a protectivelayer comprising 1.5 g/m² of gelatin and 0.3 g/m² of polymethylmethacrylate grains (having a mean grain size of 2.5 μm) along with thefollowing surfactants.

Surfactants Used ##STR40##

Samples thus prepared were exposed with a tungsten light of 3200° K.through an optical wedge and a contact screen (150L Chain-Dot Model,produced by Fuji Photo Film Co., Ltd.) and then developed with thefollowing Developer (A) at 34° C. for 30 seconds, fixed rinsed withwater and dried.

The thus processed samples were evaluated with respect to the dotgradation and halftone dot quality thereof. Dot gradation is representedby the following formula: ##EQU2##

Halftone dot quality was evaluated visually by five ranks, in which "5"is the best and "1" is the worst. The ranks "5" and "4" mean to bepractical as a halftone plate for photomechanical process; the rank "3"means to be the limit for practical use; and the ranks "2" and "1" meanto be impractical.

    ______________________________________                                        Developer (A)                                                                 ______________________________________                                        Hydroquinone             50.0   g                                             N-methyl-p-aminophenol   0.3                                                  Sodium Hydroxide         18.0                                                 5-Sulfosalicylic Acid    55.0                                                 Potassium Sulfite        110.0                                                Disodium Ethylenediaminetetraacetate                                                                   1.0                                                  Potassium Bromide        10.0                                                 5-Methylbenzotriazole    0.4                                                  2-Mercaptobenzimidazole-5-sulfonic Acid                                                                0.3                                                  Sodium 3-(5-Mercaptotetrazole)-benzene-                                                                0.2                                                  sulfonate                                                                     N-n-Butyldiethanolamine  15.0                                                 Sodium Toluenesulfonate  8.0                                                  Water to make            1      liter                                         pH adjusted with potassium hydroxide to                                                                11.6                                                 ______________________________________                                    

                  TABLE 1                                                         ______________________________________                                                                Dot        Halftone                                               Redox       Gradation  Dot                                        Sample No.  Compound    (ΔlogE)                                                                            Quality                                    ______________________________________                                        1   Comparative --          1.23     3                                            Sample, 1-a                                                               2   Comparative Comparative 1.30     4                                            Sample, 1-b Compound A                                                    3   Comparative Comparative 1.21     3                                            Sample, 1-c Compound B                                                    4   Comparative Comparative 1.27     3                                            Sample, 1-d Compound C                                                    5   Comparative Comparative 1.25     3                                            Sample, 1-e Compound D                                                    6   Comparative Comparative 1.45     5                                            Sample, 1-f Compound E                                                    7   Sample of   Compound 1  1.45     5                                            Invention, 1-1                                                            8   Sample of   Compound 3  1.45     5                                            Invention, 1-2                                                            9   Sample of   Compound 4  1.53     5                                            Invention, 1-3                                                            10  Sample of   Compound 5  1.54     5                                            Invention, 1-4                                                            11  Sample of   Compound 6  1.52     5                                            Invention, 1-5                                                            12  Sample of   Compound 8  1.48     5                                            Invention, 1-6                                                            13  Sample of   Compound 11 1.50     5                                            Invention, 1-7                                                            14  Sample of   Compound 13 1.51     5                                            Invention, 1-8                                                            15  Sample of   Compound 14 1.50     5                                            Invention, 1-9                                                            16  Sample of   Compound 33 1.45     5                                            Invention, 1-10                                                           ______________________________________                                    

Comparative compounds used above are as follows:

Comparative Compound (A)

Compound No. 28 described in JP-A-61-213847. ##STR41##

Comparative Compound (B)

Compound No. 2 described in JP-A-62-260153. ##STR42##

Comparative Compound (C)

Compound No. 10 described in JP-A-64-88451. ##STR43##

Comparative Compound (D)

Compound No. 13 described in JP-A-64-72140. ##STR44##

Comparative Compound (E)

This is described in prior Japanese Patent Application No. 2-62337.##STR45##

As is obvious from the results in Table 1 above, all the samples of thepresent invention and Comparative Sample (1-f) had a broad halftonegradation latitude and a high halftone dot quality.

EXAMPLE 2

A large number of sheets of each of 16 samples of Example 1 weredeveloped in accordance with the condition mentioned below, to prepare16 kinds of fatigued developers (B-1) to (B-16), respectively.

Processing Condition

20 liters of Developer (A) was kept at 34° C. Each sample sheet having asize of 50.8 cm×60 cm was exposed to have a blackened density of 80%.Each of the thus exposed sheets were developed with the developer in anamount of 200 sheets a day, whereupon the development time for allsheets was 30 seconds. Thus, 16 kinds of fatigued developers wereprepared.

A fresh Developer (A) and the thus fatigued 16 developers were used.Each sample was exposed in the same manner as in Example 1 and thendeveloped with the fresh developer and the fatigued developer. Thedifference in the photographic sensitivity between the sample asprocessed with the fresh developer and that processed with the fatigueddeveloper (Δlog E₁) was obtained and shown in Table 2 below. Thephotographic density (log E) is a logarithmic number of the amount ofexposure necessary for giving a density of 1.5.

Next, a commercial film of GRANDEX Film GA100 (product by Fuji PhotoFilm Co.) was exposed in the same manner as in Example 1 and thendeveloped with the fresh developer (A) and with each of the fatigueddevelopers (B-1) to (B-16). The difference in the photographicsensitivity between the commercial film sample as processed with thefresh developers (B-1) to (B-16) (Δlog E₂) was obtained and shown inTable 2 below.

From the results in Table 2, it is understood that the fluctuation ofthe photographic sensitivity of each of the samples of the presentinvention is far smaller than that of the comparative samples (2-b) to(2-f). The level of the fluctuation of the photographic sensitivity ofeach of the samples of the present invention is almost the same as thatof the comparative sample (2-a) containing no redox compound.

                  TABLE 2                                                         ______________________________________                                                        Fluctuation of Photographic                                                   Sensitivity of Sample as                                                      Processed with Fatigued                                                       Developer                                                                           Indicated GRANDEX Film                                              Fatigued  Sample    GA-100                                        Sample No.  Developer (Δlog E.sub.1)                                                                    (Δlog E.sub.2)                          ______________________________________                                        1   Comparative B1        -0.05   -0.08                                           Sample, 2-a                                                               2   Comparative B2        -0.29   -0.33                                           Sample, 2-b                                                               3   Comparative B3        -0.25   -0.27                                           Sample, 2-c                                                               4   Comparative B4        -0.24   -0.25                                           Sample, 2-d                                                               5   Comparative B5        -0.36   -0.39                                           Sample, 2-e                                                               6   Comparative B6        -0.35   -0.35                                           Sample, 2-f                                                               7   Sample of   B7        -0.07   -0.10                                           Invention, 2-1                                                            8   Sample of   B8        -0.06   -0.11                                           Invention, 2-2                                                            9   Sample of   B9        -0.08   -0.12                                           Invention, 2-3                                                            10  ample of    B10       -0.08   -0.13                                           Invention, 2-4                                                            11  Sample of   B11       -0.08   -0.12                                           Invention, 2-5                                                            12  Sample of   B12       -0.06   -0.11                                           Invention, 2-6                                                            13  Sample of   B13       -0.07   -0.10                                           Invention, 2-7                                                            14  Sample of   B14       -0.09   -0.14                                           Invention, 2-8                                                            15  Sample of   B15       -0.06   -0.10                                           Invention, 2-9                                                            16  Sample of   B16       -0.05   -0.09                                           Invention, 2-10                                                           ______________________________________                                    

EXAMPLE 3 Preparation of Light-Sensitive Emulsion (B)

An aqueous silver nitrate solution and an aqueous sodium chloridesolution were added simultaneously to an aqueous gelating solution keptat 50° C., in the presence of 5.0×10⁻⁶ mol of (NH₄)₃ RhCl₆ per mole ofsilver, and then soluble slats were removed from the reaction system bya conventional method well known in the technical field. Gelatin wasadded thereto and, without chemical ripening of the emulsion, astabilizer of 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene was addedthereto. The thus prepared emulsion was a monodispersed emulsion ofcubic grains having a mean grain size of 0.15 μm.

Coating of Light-Sensitive Emulsion Layers First Layer

To the emulsion (B) were added a nucleating agent of Hydrazine CompoundI-8 (75 mg/m²), 5-methylbenzotriazole (5×10⁻³ mol/mol of Ag), polyethylacrylate latex (30 wt. % to gelatin) and 1,3-divinylsulfonyl-2-propanol(2.0 wt. % to gelatin). The resulting composition was coated on asupport in an amount of 3.5 g/m² as silver.

Second Layer

Gelatin (1.0 g/m²) was coated.

Third Layer

To the emulsion (B) were added 5-methylbenzotriazole (5×10⁻³ mol/mol ofAg), polyethyl acrylate latex (30 wt. % to gelatin),1,3-divinylsulfonyl-2-propanol (2 wt. % to gelatin),1,3-divinylsulfonyl-2-propanol (2 wt. % to gelatin) and redox compound(shown in Table 3 below). The resulting composition was coated in anamount of 0.4 g/m² as silver.

Fourth Layer (Protective Layer)

A protective layer comprising 1.5 g/m² of gelatin, 0.3 g/m² of a matagent of polyethyl methacrylate grains (having a mean grain size of 2.5μM) and, as coating aids, the following surfactants, stabilizer andultraviolet absorbing dye, was coated and dried.

Surfactants ##STR46## Stabilizer

Thioctic Acid

Ultraviolet Absorbent ##STR47##

The thus prepared samples were imagewise exposed through the originalshown in FIGURE by the use of a daylight printer P-607 Model(manufactured by Dai-Nippon Screen Co.) and then developed at 38° C. for20 seconds, fixed, rinsed with water and dried. The thus processedsamples were evaluated with respect to the quality of the superimposedletter image formed thereon by way of 5-rank evaluation.

For the 5-rank superimposed letter image evaluation, the photographicmaterial sample was properly exposed through the original of FIGURE sothat 50% of the dot area of the original could be 50% of the dot area ofthe reproduced image on the sample by contact dot-to-dot work. The rank"5" in the evaluation indicates that 30 micron-letters were wellreproduced under the condition and the superimposed letter image qualitywas excellent. The rank "1" therein indicates that only letters of 150microns or more were reproduced under the same condition and thesuperimposed letter image quality was bad. The other ranking of from "4"to "2" between the ranks "5" and "1" was conducted by functionalevaluation. The ranks "3" or more indicate the practical level.

The results obtained are shown in Table 3 below. As is obvioustherefrom, the samples of the present invention had an excellentsuperimposed letter image quality.

In addition, the samples were tested with respect to the photographicproperty as processed with a fatigued developer in the same manner as inExample 2. As a result, all the samples of the present invention gavegood results, like those in Example 2.

                  TABLE 3                                                         ______________________________________                                                                  Super-                                                       Redox Compound   Imposed                                                                   Amount Added                                                                              Letter Image                                Sample     Kind       (mol/m.sup.2)                                                                             Quality                                     ______________________________________                                        Comparative                                                                              Comparative                                                                              2.0 × 10.sup.-5                                                                     3                                           Sample, No. 6                                                                            Compound B                                                         Sample of  Compound 1 2.0 × 10.sup.-5                                                                     4                                           Invention, No.                                                                3-1                                                                           Sample of  Compound 3 2.0 × 10.sup.-5                                                                     4                                           Invention, No.                                                                3-2                                                                           Sample of  Compound 4 2.0 × 10.sup.-5                                                                     5                                           Invention, No.                                                                3-3                                                                           Sample of  Compound 5 2.0 × 10.sup.-5                                                                     5                                           Invention, No.                                                                3-4                                                                           Sample of  Compound 6 2.0 × 10.sup.-5                                                                     5                                           Invention, No.                                                                3-5                                                                           Sample of  Compound 8 2.0 × 10.sup.-5                                                                     5                                           Invention, No.                                                                3-6                                                                           ______________________________________                                    

EXAMPLE 4

Samples of the Invention, 4-1 to 4-7 were prepared in the same manner asSample 1-1 described in Example 1 except for using each of the hydrazinecompounds of formula (I) shown in Table 4 below in place of HydrazineCompound (c) used in Example 1.

The resulting samples were evaluated with respect to the dot gradation,and the halftone dot quality in the same manner as in Example 1 as wellas the photographic sensitivity when developed with a fatigued developerin the same manner as in Example 2. The results obtained are shown inTable 4 below.

                                      TABLE 4                                     __________________________________________________________________________             Hydrazine Compound                                                            of Formula (I)         Fluctuation in                                               Amount                                                                              Dot   Halftone                                                                           Photographic Sensitivity                               Compound                                                                            Added Gradation                                                                           Dot  as Processed with Fatigued                    Sample No.                                                                             No.   (mol/m.sup.2)                                                                       (ΔlogE)                                                                       Quality                                                                            Developer                                     __________________________________________________________________________    1 Sample of                                                                            I-2   2.8 × 10.sup.-5                                                               1.38  5    -0.11                                           Invention, 4-1                                                              2 Sample of                                                                            I-10  2.8 × 10.sup.-5                                                               1.45  5    -0.08                                           Invention, 4-2                                                              3 Sample of                                                                            I-13  2.8 × 10.sup.-5                                                               1.48  5    -0.07                                           Invention, 4-3                                                              4 Sample of                                                                            I-22  2.8 × 10.sup.-5                                                               1.39  5    -0.10                                           Invention, 4-4                                                              5 Sample of                                                                            I-20  4.0 × 10.sup.-6                                                               1.47  5    -0.06                                           Invention, 4-5                                                              6 Sample of                                                                            I-25  4.0 × 10.sup.-6                                                               1.50  5    -0.07                                           Invention, 4-6                                                              7 Sample of                                                                            I-27  4.0 × 10.sup.-6                                                               1.48  5    -0.08                                           Invention, 4-7                                                              __________________________________________________________________________

It is understood from the results shown in Table 4 that excellentphotographic having a broad dot gradation, good halftone quality andless fluctuation in photographic sensitivity when developed with afatigued developer can be obtained by using a hydrazine compoundrepresented by formula (I) of the present invention.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A silver halide photographic material comprisinga compound of general formula (2): ##STR48## wherein time is a divalentlinking group; t represents 0 or 1; Y-L-Z is a development inhibitor,wherein Y is a divalent group comprising a hetero atom through which Ybonds to the moiety ##STR49## L is a divalent group which is capable ofbeing cleaved by a component of a developer and Z is a functional groupthat expresses a development inhibiting effect wherein, after cleavageof L, a resulting compound of Y-L-Z has a small development inhibitingactivity; R₁ is an aliphatic group or an aromatic group; G₁ is ##STR50##G₂ is a mere bond, --O--, --S-- or ##STR51## R₂ has the same meaning asR₁ or is a hydrogen atom; when said compound has plural R₂ 's they arethe same or different; and one of A₁ and A₂ is a hydrogen atom and theother is a hydrogen atom, an acyl group, an alkylsulfonyl group or anarylsulfonyl group; and a hydrazine compound represented by the formula(I): ##STR52## wherein R₁₁ is an aliphatic group or an aromatic group;R₁₂ is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group,an aryloxy group, an amino group or a hydrazino group; G₁₁ is ##STR53##a thiocarbonyl group or an iminomethylene group; A₁₁ and A₁₂ are bothhydrogen atoms, or one is a hydrogen atom, and the other is analkylsulfonyl group, an arylsulfonyl group or an acyl group; and R₁₃ hasthe same meaning as R₁₂, and R₁₃ is the same as or different from R₁₂.2. The silver halide photographic material of claim 1, wherein themoiety -Y-L-Z in formula (2) is represented by formula (3):

    -Y.sub.1 -Y.sub.2 -L-Z                                     (3)

wherein R₁ is --O--, --S--, -Se-, -Te- or ##STR54## R₃ is a hydrogenatom or has the same meaning as R₁ in the formula (2); Y₂ is analiphatic group, an aromatic group, or a substituted divalent groupformed by combining an aliphatic or aromatic group and --O--, --S--,-Se-, ##STR55## --CO--, --SO-- or --SO₂ --; R₄ has the same meaning asR₃ ; and L and Z have the same meanings as in formula (2).
 3. The silverhalide photographic material of claim 1, wherein the moiety -Y-L-Z informula (2) is represented by formula (4): ##STR56## wherein L and Zhave the same meanings as in formula (2); Y₄ is a single bond or is analiphatic group, an aromatic group or a substituted divalent groupformed by combining an aliphatic or aromatic group and --O--, --S--,-Se-, ##STR57## --CO--, --SO-- or --SO₂ --; R₄ is a hydrogen atom or hasthe same meaning as R₁ in formula (2); and Y₃ is a non-metallic atomicgroup that forms a nitrogen-containing hetero ring with the nitrogenatom in the formula (4).
 4. The silver halide photographic material ofclaim 2, wherein the moiety L-Z in formula (3) is represented by formula(5):

    -L.sub.3 -L.sub.4 -Z                                       (5)

wherein L₃ is ##STR58## R₅ is a hydrogen atom or has the same meaning asR₁ in formula (2); Z has the meaning as in formula (2); and L₄ is asingle bond or has the same meaning as Y₂ in formula (3).
 5. The silverhalide photographic material of claim 2, wherein the moiety L-Z informula (3) is represented by formula (6): ##STR59## wherein L₅ is##STR60## or --SO₂ --; L₆ is a monovalent group, two L₆ 's are the sameor different, are bonded to each other to form a ring or one or both ofthe two L₆ 's are bonded to Y of formula (2) to form a ring or apolycyclic ring; L₇ is --O--, --S-- or --SO₂ --; L₄ is a single bond orhas the same meaning as Y₂ in formula (3); and Z has the same meaning asin formula (2).
 6. The silver halide photographic material of claim 2wherein the moiety L-Z in formula (3) is represented by formula (7):##STR61## wherein L₄ is a single bond or has the same meaning as Y₂ informula (3), L₅ is ##STR62## or --SO₂ --, L₆ is a monovalent group, twoL₆ 's are the same or different, are bonded to each other to form a ringor one or both of the two L₆ 's are bonded to Y of formula (2) to form aring or a polycyclic ring, L₇ is --O--, --S-- or --SO₂ -- and Z has thesame meaning as in formula (2).
 7. The silver halide photographicmaterial of claim 2, wherein the moiety L-Z in formula (3) isrepresented by formula (8): ##STR63## wherein L₄ is a single bond or hasthe same meaning as Y₂ in formula (3); Z has the same meaning as informula (2); L₅ is ##STR64## or --SO₂ --; L₈ has the same meaning as Y₁in formula (3); and L₉ is a non-metallic atomic group that forms acyclic structure with the nitrogen atom, L₅ and carbonyl group.
 8. Thesilver halide photographic material of claim 3, wherein the moiety L-Zin formula (4) is represented by formula (5):

    -L.sub.3 -L.sub.4 -Z                                       (5)

wherein L₃ is ##STR65## R₂ is a hydrogen atom or has the same meaning asR₁ in formula (2); Z has the same meaning as in formula (2); and L₄ is asingle bond or is an aliphatic group, an aromatic group or a substituteddivalent group formed by combining an aliphatic or aromatic group and--O--, --S--, -Se-, ##STR66## --CO--, SO-- or --SO₂ --; and R₄ is ahydrogen atom or has the same meaning as R₁ in formula (2).
 9. Thesilver halide photographic material of claim 3, wherein the moiety L-Zin formula (4) is represented by formula (6): ##STR67## wherein L₅ is##STR68## or --SO₂ --; L₆ is a monovalent group, two L₆ 's are the sameor different, are bonded to each other to form a ring or one or both ofthe two L₆ 's are bonded to Y of formula (2) to form a ring or apolycyclic ring; L₇ is --O--, --S-- or --SO--; L₄ is a single bond or isan aliphatic group, an aromatic group or a substituted divalent groupformed by combining an aliphatic or aromatic group and --O--, --S--,-Se-, ##STR69## --CO--, --SO--]or --SO₂ --; R₄ is a hydrogen atom or hasthe same meaning as R₁ in formula (2); and Z has the same meaning as informula (2).
 10. The silver halide photographic material of claim 3,wherein the moiety L-Z in formula (4) is represented by formula (7):##STR70## wherein L₄ is a single bond or is an aliphatic group, anaromatic group or a substituted divalent group formed by combining analiphatic or aromatic group and --O--, --S--, -Se-, ##STR71## --CO--,--SO-- or --SO₂ --; R₄ is a hydrogen atom or as the same meaning as R₁in formula (2), L₅ is ##STR72## or --SO₂ --, L₆ is a monovalent group,two L₆ 's are the same or different, are bonded to each other to form aring or one or both of the two L₆ 's are bonded to Y of formula (2) toform a ring or a polycyclic ring, L₇ is --O--, --S-- or --SO₂ -- and Zhas the same meaning as in formula (2).
 11. The silver halidephotographic material of claim 3, wherein the moiety L-Z in formula (4)is represented by formula (8): ##STR73## wherein L₄ is a single bond oris an aliphatic group, an aromatic group or a substituted divalent groupformed by combining an aliphatic or aromatic group and --O--, --S--,-Se-, ##STR74## --CO--, --SO-- or --SO₂ --; R₄ is a hydrogen atom or hasthe same meaning as R₁ in formula (2); Z has the same meaning as informula (2); L₅ is ##STR75## or --SO₂ --; L₈ is --O--, --S--, -Se-, -Te-or ##STR76## R₃ is a hydrogen atom or has the same meaning as R₁ informula (2); and L₉ is a non-metallic atomic group that forms a cyclicstructure with the nitrogen atom, L₅ and carbonyl group.